Process for the production of polycondensation products of aromatic diazonium compounds

ABSTRACT

1. A PROCESS FOR THE PREPARATION OF A POLYCONDENSATION PRODUCT OF AN AROMATIC DIAZONIUM COMPOUND WHICH COMPRISES REACTING IN THE ABSENCE OF ADDED FORMALDEHYDE AT LEAAST ONE A-N2X COMPOUND AND AT LEAST ONE B1 COMPOUND OF THE FORMULA   E(-CHRA-ORB)M   IN WHICH A-N2X IS A RAICAL OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF A COMPOUND OF THE FRMULA   (R1-R2)P-R2-N2-X AND (-Y-R1&#39;&#39;-)&gt;R2-N2-X   WHEREIN R1 IS A PHENYL OR NAPHTHYL GROUP R&#39;&#39;1 IS A PHENYLENE OR NAPHTHYLENE GROUP R2 IS A PHENYLENE GROUP R3 IS A SINGLE BOND OR ONE OF THE GROUPS -(CH2)Q-NR4-O-(CH2)R-NR4-S-(CH2)R-NR4-S-CH2-CO-NR4-O-R5-O-O-O- OR -CO-NR4THE LEFT-HAND FREE VALENCE OF THE SPECIFFIED GROUPS IS ATTACHED TO R1 AND THE RIGHT-HAND FREE VALENCE IS ATTACHED TO R2, WHEREIN Q IS A NUMBER FROM 0 TO 5 R IS A NUMBER FROM 2 TO 5 R4 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN ALKYL WITH 1 TO 5 CARBON ATOMS, ARALKYL WITH 7 TO 12 CABON ATOMS, AND ARYL WITH 6 TO 12 CARBON AOMS, R5 IS AN ARYLENE GROUP HAVING 6 TO 12 CARBON ATOMS Y IS ONE OF THE GROUPS -NH-, AND -OX IS AN ANION P IS A NUMBER FROM 1 TO 3 E IS A RAICAL OBTAINED BY SPLITTING OFF OF M H ATOMS FROM A COMPOUND FROM THE GROUP CONSISTING OF AROGROUGROUP SELECTED FROM THE GROUP CONSISTING OF AROMATIC AMINES, PHENOLS, THIOPENOLS, PHENOL ETHERS, AROMATIC THIOETHERS, AROMATIC HETEROCYCLIC COMPOUNDS, AROMATIC HYDROCARBONS AND ORGAIC ACID AMIDES, RA IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND PHENYL, RB IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND ALKYL CNH2N+1CO- WHEREIN N IS FROM 0 TO 3 AND A PHENYL GROUP, AND M IS AN INTEGER FROM 1 TO 10 IN A STRONG ACIDIC CONDENSATION MEDIUM AND UNDER CONDENSATION CONDITIONS SUFFICIENT TO PRODUCE A POLYCONDENSATION PRODUCT OF AN AROMATIC DIAZONIUM COMPOUND CONTAINING, ON THE AVERAGE, ABOUT 0.1 TO 50 B1 UNITS PER UNIT OF A-N2X.

United States Patent PROCESS FOR THE PRODUCTION OF POLYCON- DENSATIONPRODUCTS OF AROMATIC DIAZO- NIUM COMPOUNDS Hartmut Steppan,Wiesbaden-Dotzheim, Germany, as-

signor to Kalle Aktiengesellschaft, Wiesbaden-Biebrich, Germany NoDrawing. Continuation of abandoned application Ser. No. 826,296, May 20,1969. This application Feb. 7, 1972, Ser. No. 224,324

Int. Cl. C07c 113/04; G03c 1/54; G031? 1/54 US. Cl. 260-441 32 ClaimsABSTRACT OF THE DISCLOSURE This invention relates to a process for thepreparation of polycondensation products of aromatic diazoniumcompounds, useful as light-sensitive coatings, particularly in thepreparation of printing plates and the like, in which at least one A--NX compound and at least one B compound of the formula:

in which: AN X is a radical of a compound selected from the groupconsisting of a compound of the formulae:

R is an aryl group of the benzene or naphthalene series R is an arylenegroup of the benzene or naphthalene series R is a phenylene group R is asingle bond or one of the groups the left-hand free valence of thespecified groups is attached to R and the right-hand free valence isattached to R wherein q is a number from 0 to r is a number from 2 to 5R is selected from the group consisting of hydrogen, alkyl with 1 to 5carbon atoms, aralkyl with 7 to 12 carbon atoms, and aryl with 6 to 12carbon atoms,

R is an arylene group having 6 to 12 carbon atoms Y is one of the groupsNH, and O' X is an anion P is a number from 1 to 3 E is a residueobtained by splitting off of m H atoms from a compound free of diazoniumgroups selected from the group consisting of aromatic amines, phenols,thiophenols, phenol ethers, aromatic thioethers, aromatic heterocycliccompounds, aromatic hydrocarbons and organic acid amides,

R is selected from the group consisting of hydrogen and phenyl,

R is selected from the group consisting of hydrogen and alkyl and acylgroups having 1 to 4 carbon atoms, and a phenyl group, and

m is an integer from 1 to 10,

3,849,392 Patented Nov. 19, 1974 ice This is a continuation ofapplication Ser. No. 826,296 filed May 20, 1969, and now abandoned.

This invention relates to a new process for the preparation oflight-sensitive compounds, the compounds prepared according to the newprocess, and to light-sensitive reproduction material, which lattercomprises a support having a reproduction layer thereon containing atleast one of the novel compounds which are light-sensitive condensationproducts of aromatic diazonium salts.

It is known to use light-sensitive aromatic diazonium compounds forsensitizing reproduction materials which are useful for the productionof single copies or printing plates.

High molecular weight diazonium salts with several diazonium groups inthe molecule have been advantageously employed, particularly in theproduction of tanned images or planographic printing forms, thereproduction layer of which is to be rendered insoluble or oleophilic bythe action of light. These diazonium compounds usually have a resinouscharacter and are obtained, for example, by the introduction ofdiazonium groups into phenol-formaldehyde condensation resins either bynitration, reduction, and diazotization or by other known reactions. Thediazo resins thus obtained have certain disadvantages, however, e.g. avery limited storability, and therefore have not become of practicalimportance.

Polyfunctional diazonium salts have been obtained in another way, i.e.,certain aromatic diazonium salts have been condensed in an acidcondensation medium with active carbonyl compounds, particularlyformaldehyde. This type of high molecular weight diazonium compound isused on a large scale in the production of reproduction materials,particularly in the production of printing forms. Of these compoundswhich are described, for example, in US. Pats. Nos. 2,063,631 and2,667,415, particularly the condensation products of diphenylaminediazonium salts with formaldehyde have become of great technicalimportance.

The preparation of such and similar diazo resins is further described inUS. Pats. Nos. 2,679,498; 3,050,502; 3,311,605; 3,163,633; 3,406,159,and 3,227,074.

The production of tanned images by combining such diazo resins withhydrophilic colloids and, if desired, dyestufls or pigments, inreproduction layers is described, for example, in US. Pats. Nos.2,100,063; 2,687,958, and 3,010,389.

By far the greatest importance, however, of this class of diazo resinsis in reproduction materials for the photomechanical production ofplanographic and oifset printing forms. The diazo resins may be employedin the reproduction layers of these materials without further additivesor, for example, in combination with water-soluble colloids or withwater-insoluble polymers which are not light-sensitive. Exemplary ofsuitable supports for such reproduction layers are Water-resistantpapers with suitable lithographic surfaces, i.e., superficiallysaponified cellulose acetate, metal supports such as aluminum, zinc,copper, brass, chromium, niobium, and tantalum; multimetal supports;lithographic stone; and the like. Metal supports are preferable for longprinting runs and aluminum is usually employed. The use of metal as asupporting material for reproduction layers containing the listed diazoresins has the disadvantage, inter alia, that the adhesion of theexposure products of the diazo resins on the metal supports usually isnot very good and, furthermore, that the metal may have a decomposingeffect on the diazo resin.

A number of suggestions have been made for avoiding these difficulties,e.g. to pretreat the metal surface with silicates (U.S. Pat. No.2,714,066), with organic polyacids (U.S. Pat. No. 3,136,636), withphosphonic acids and their derivatives (U.S. Pat. No. 3,220,832), withpotassium hexafiuorozirconate (U.S. Pat. No. 2,946,683), furthermore touse diazo resins prepared in phosphoric acid (U.S. Pat. No. 3,235,384),to add phosphoric acid to the diazo resins and to use them in a metalsalt-free state (U.S. Pat. No. 3,236,646), to use anodized aluminumsurfaces, and the like.

Despite finding wide technical use, the known diazo resins have otherdisadvantages. With the low molecular weight condensates which areadvantageously employed, with respect to storability, onlyunsatisfactory ink acceptance of the exposure products is achieved onnon-metallic supports into which the mass can easily penetrate, e.g. onsuperficially saponified cellulose acetate film.

Another drawback of the known diazo resins lies in that their usuallyemployed double salts with Zinc chloride, and particularly the metalsalt-free products containing phosphoric acid or other acids, yieldreproduction layers having a high sensitivity to moisture and thus tofingerprints. In the case of careless handling, the reproduction layermay be easily damaged.

For overcoming this drawback it has been suggested in US. Pat. No.3,300,309, for example, to react the diazo resins with certain phenoliccoupling components to obtain addition products sparingly soluble inwater and yielding reproduction layers which are less sensitive tomoisture. These addition products, which contain relatively loose bondsof the nature of a salt or complex, can be easily decomposed again, e.g.by organic solvents, and their stability thus is not sufficient underall conditions.

Furthermore, the light-sensitivity is not satisfactory, particularly inthe case of the known diazo resins which have excellent thermostability,e.g. condensation products of 3-alkoxy-4-diazo-diphenylamine withformaldehyde.

A common disadvantage of the diazo resins hitherto preferablytechnically employed, furthermore resides in the fact they can beseparated only with difficulty in a metal salt-free form, e.g. aschlorides, sulfates, or as salts of simple organic sulfonic acids, andtheir salts are often only insufiiciently soluble in organic solvents.

The drawbacks of the prior art can be overcome, or at least considerablyreduced, by using new diazo condensation products instead of thediazonium salts hitherto employed for the above applications.

In co-pending application Ser. No. 826,297, filed May 20, 1969, and nowabandoned, by Leon A. Tencher there are described and claimed novellight-sensitive compounds and a light-sensitive reproduction materialwhich comprises a support having a reproduction layer thereon, thelatter containing at least one of the novel compounds which arelight-sensitive condensation products of aromatic diazonium compoundswhich condensation products include at least one unit each of thegeneral types:

which are connected by a bivalent intermediate member derived from acondensable carbonyl compound and wherein A is a radical of a compoundcontaining at least two aromatic carbocyclic and/or aromaticheterocyclic nuclei, which compound is capable of condensation in atleast one position with an active carbonyl compound in an acid medium,

D is a diazonium salt group attached to an aromatic carbon atom of A,

n is an integer from 1 to 10, and

B is a radical of a compound free of diazonium groups, which compound iscapable of condensation in at least one position with an active carbonylcompound in an acid medium,

mula

R is selected from the group consisting of H, an alkoxy group havingfrom 1 to 4 carbon atoms, and a 2-hydroxy-ethoxy group, and

X is the anion of the diazonium salt,

wherein and at least one compound of the general formula R z z) 11wherein n is an integer from 1 to 4,

R is a residue produced by the splitting off of n hydrogen atoms from adiphenyl ether, and

R is selected from the group consisting of H, an alkyl group with 1 to 4carbon atoms, and an acyl group with 1 to 4 carbon atoms,

said condensation product containing, on the average, 0.25 to 0.75 unitderived from R(CH OR per diazo group.

The first-mentioned co-pending application, furthermore, describes andclaims a process for the preparation of the novel light-sensitivecondensation products which process comprises condensing, in a stronglyacid medium, at least one aromatic diazonium compound of the generalformula A(D) and at least one compound B, the symbols having theabove-indicated meanings, with at least one active carbonyl compound, ina free form, or with agents producing such a carbonyl compound.

This process often may be employed advantageously when the componentsA(D) and B are sufiiciently soluble in the condensation medium. Whereasmany diazo compounds exhibit this solubility, only part of compo nents Bconcerned are sufiiciently soluble in the condensation mixture.

But unfortunately such compounds B as yield mixed condensates leading toreproduction materials with particularly advantageous properties have avery low solubility in the strong acids of high concentration which arepreferred as condensation media. This applies, for example, to thearomatic hydrocarbons, phenol ethers, and certain non-basic heterocycliccompounds.

A number of such compounds are sufiiciently soluble in 96 to 98%sulfuric acid which is highly effective as a condensation medium, butsulfonation of components B easily occurs as a side-reaction in thismedium and the desired mixed condensates are not obtained in thesecases. Mesitylene, anisole, and diphenyl ether, for example, dissolve in96 to 98% sulfuric acid at to C. with sulfonation. This trouble doesalmost not occure in sulfuric acid but, on the other hand, thesolubility of the mentioned preferred second components is relativelylow.

Furthermore, highly concentrated sulfuric acid is not preferred as areaction medium since a number of diazo compounds, e.g. the3-alkoxy-diphenylamine-4-diazonium salts yielding particularly valuablemixed condensates are very sensitive to this acid. 80 to phosphoric acidis a substantially more gentle condensation medium but the solubility ofmany preferred components B is particularly low in this acid.

It is possible to achieve a certain improvement of the homogeneityduring condensation by the addition of organic solvents, e.g. glacialacetic acid or methanol, but it has to be taken into account that theefiiciency of the condensation medium often is decreased too muchthereby, in comparison with the pure acid, and the danger ofside-reactions occurs.

Furthermore, when using components A(-D) and B having very difierentreaction speeds with respect to the active carbonyl compound, it is noteasy to prevent the formation of homocondensates of the more rapidlyreacting component and to perform condensation in a manner such thatcondensation products of a relatively uniform structure are obtained.Due to the extra-ordinarily numerous reaction possibilities of the threereaction partners, it is diflicult to obtain always the samecondensation products from the same starting products. If condensationproducts with exactly reproducible properties are to be obtained, itgenerally is necessary to carefully keep to the same reactionconditions.

These and other difficulties during the production of diazo mixedcondensates are avoided or at least considerably diminished if thecondensation products are produced according to the process describedbelow, which is the object of the present invention.

The present invention relates to a new process for the preparation oflight-sensitive aromatic diazo condensation products of theabove-indicated general type, to the compounds obtained according to thenew process and the use of the compounds in light-sensitive reproductionmaterial which process comprises reacting at least one A(D) compound andat least one B compound of the general formula E(CHR,,OR in a stronglyacid medium, wherein A is a radical of a compound containing at leasttwo members selected from the group consisting of an aromatic ring and aheterocyclic ring of aromatic nature,

D is a diazonium salt group linked to an aromatic carbon atom of A,

n is an integer from 1 to 10,

E is a residue obtained by the splitting-off of m H atoms from acompound free of diazonium groups and being capable of condensation inat least one position with an active carbonyl compound in an acidmedium,

R is selected from the group consisting of hydrogen,

alkyl, aryl, and heterocyclic groups,

R is selected from the group consisting of hydrogen, alkyl or acylgroups having 1 to 4 carbon atoms, and a phenyl group, and

m is an integer from 1 to 10,

the condensation product containing about 0.1 to 50 units derived from Bper unit of A(D) In the above formula, R is preferably hydrogen and Rpreferably hydrogen, methyl, ethyl or acetyl.

Although longer alkyl chains or higher acyl groups may be used, theyreduced normally in an undesirable manner the solubility of thecomponent B in the condensation mixture and thus impede the condensationprocess and render it more expensive.

Depending on the size of the molecule, the value of m may range from 1to about 10. Preferably it does not exceed 4. It can be assumed thatduring condensation component B reacts completely or partially withcomponent A(D) or with itself (particularly when an excess of componentB is present), with intermolecular splitting off of R OH, thus formingthe condensation products. The behavior and the composition of thereaction products can be explained by such a condensation process.

The condensation according to the process of the invention proceedsurprisingly smoothly, i.e. in many cases already under very moderateconditions, e.g. at to 40 C. in 80 to 100% phosphoric acid practicallyquantitatively with the formation of mixed condensates.

The process of the invention for the production of mixed condensatesfrom diazo compounds A(D) and B inter alia, has the following advantagesover the reaction of A(D) and B with carbonyl compound:

(1) In cases where components B having very different reaction speedswith respect to the diazo compound are employed, the transition tocompound B generally favors the mixed condensation with respect to thehomocondensation of the more rapidly condensing partner.

(2) In many cases, condensation of A(D) with B is possible under moremoderate conditions than is the corresponding condensation of A(-D) B,and active carbonyl compound. This is of advantage when A(D) or B aresensitive to highly active condensation media, e.g. concentratedsulfuric acid.

(3) In the case of condensation of A(D) with B it generally is possibleto obtain more uniform and better defined condensation products of abetter quality and in a higher yield.

(4) The compounds B generally are more readily soluble in the usualstrongly acid condensation media than is the parent compound B. Anaddition of organic solvents during condensation thus can be dispensedwith in most cases. Especially suitable is the application oflow-melting, particularly liquid components B The low alkyl ethers (Ralkyl), therefore, are a preferred group of components B (5) The processis less susceptible to trouble and substantially more easilyreproducible since it can be performed in many cases in the homogeneousphase.

A group of mixed condensates prepared according to the process of theinvention also distinctly differs in substance characteristics from themixed condensates prepared according to the process of the co-pendingapplication from the corresponding components A(D) B and formaldehyde.This group derives from components B which, preferably under moderatecondensation conditions, e.g. in to phosphoric acid at temperatures from10 to 40 C., do not undergo substantial splitting 01f of formaldehyde.

This group particularly includes such components B as derive from parentcompounds of the series of the aromatic hydrocarbons, the phenol ethers,the aromatic thioethers, and the non-basic heterocycles, e.g.diphenylene sulfide, diphenylene oxide, phenoxathiine, and the like.These parent compounds have as a common feature the property to undergoa condensation reaction with formaldehyde not in an alkaline medium butonly in an acid medium. It also should be noted, however, that phenolalcohols, obtained in an alkaline medium from phenols or the ethers andesters thereof with a free phenolic OH group undergo a surprisinglyslight splitting off of formaldehyde under the above-mentioned moderateconditions.

N-methylol compounds as well as the ethers and esters thereof, however,are more easily accessible to the splitting oif of formaldehyde undercondensation conditions.

The mentioned group of the condensation products obtained according tothe process of the invention differs in the arrangement of the unitsfrom the condensates obtained from A(D) B, and formaldehyde. In thecondensates of the invention, the units A(----D) are linked togethersubstantially only via linking members derived from one or moremolecules B This means that the distance from diazo group to diazo groupin the mixed condensate normally has at least a minimum value caused bythe structure of E, whereas condensates prepared according to theprocess of the co-pending application contain the units A(--D) and Blinked by methylene bridges substantially in a statistical distributionor in other mixed arrangements which are influenced by the manner inwhich A(D),,, B, and formaldehyde are introduced into the acid. Suchproducts, of course, also include condensates with more units A(D) onlylinked to one another by methylene bridges, a type which practicallydoes not occur in the condensates prepared according to the process ofthe invention since the mentioned components B are not to be regarded asagents splitting oil formaldehyde under moderate condensationconditions, e.g. 10 to 40 C. and 80 to 100% phosphoric acid as thecondensation medium.

Within the scope of this invention, the most important process productsare those in the production of which B is used in such a quantity thatat least one -CHR OR group occurs per each molecule A(D) Particularlypreferable are such mixed condensates as contain about 0.5 to 2 moles ofB per unit of A(--D) Within this large group, there should be pointedout another preferred group of condensation products which have beenprepared under moderate condensation conditions from the above-mentionedcomponents B practically not splitting otf formaldehyde duringcondensation and from easily condensable diazonium salts of the generalformula R is a phenyl group either unsubstituted or substituted by oneor more alkyl or alkoxy groups,

R is a benzene ring which, in addition to the diazonium group, may carryone or two identical or different substituents which may be halogenatoms, alkyl groups with 1 to 4 carbon atoms, or alkoxy groups with l to5 carbon atoms, and

R is a homopolar bond or one of the members Of the last preferred groupof condensation products prepared according to the invention such areparticularly preferred as are obtained with chemically uniform compoundsB i.e. not with isomer mixtures.

Such particularly preferable compounds B aredi-methoxymethyl-diphenylether, particularly the 4,4-

isomer,

di-methoxymethyl-diphenylsulfide, particularly the 4,4-

isomer,

di-methoxymethyl-diphenyl, particularly the 4,4'-isomer,

4,4'-bis-methoxymethyl-diphenylmethane.

By the use of these uniform components B in addition to theabove-mentioned predominantly alternating structure of the condensates,a degree of uniformity of the products is achieved as it usually can notbe achieved by the condensation of A(D) and formaldehyde. The mixedcondensates prepared according to the process of the invention generallyhave a more uniform chemical structure than have those preparedaccording to the lastmentioned process. It also is possible according tothe process of the invention to obtain mixed condensates of highermolecular weights already under more moderate conditions.

Therein and in the more uniform structure of the process products of theinvention there might be the cause of the particularly easy separabilitythereof from aqueous solutions in the form of scarcely soluble salts,the high yields in the production and the better application propertiesthereof in light-sensitive reproduction layers.

This particularly applies to the condensation products from3-alkoxy-diphenylamine-4-diazonium salts and 0.75 to 2 moles of B Bderiving from diphenyl ether, diphenyl sulfide, diphenyl, and diphenylmethane, m being 2, and uniform compounds B being used, particularlythose the CHR OR groups of which are in p,ppositions.

In the case of particularly reactive basic compounds B(=EH) thecomponents B may be prepared by the addition of active carbonylcompounds in an alkaline or neutral medium to the basic compounds (suchas phenols, sulfonamides or carbonamides). The primarily formed additionproducts of the alcohol type may be easily converted into thecorresponding ethers or esters which are normally more stable.

In the case of basic compounds B which do not form addition productswith active carbonyl compounds in an alkaline medium, but react in anacid medium (such as aromatic hydrocarbons and phenol ethers), anindirect production of the compounds B is advisable, since it isnormally impossible, when reacting a compound B with an active carbonylcompound in an acid medium, to separate the intermediate products of thetype B in a Satis factory yield because they further react too rapidlyunder the reaction conditions prevailing.

The indirect preparation of the compounds of type B may be carried outby the following methods, e.g.:

(1) By halogenmethylation of compounds B and subsequent conversion ofthe halogen methyl compounds obtained into the corresponding alcohols,esters or ethers.

(2) By side-chain halogenation of compounds B carrying methyl groups inthe aromatic nucleus, i.e. conversion of these methyl groups intomonohalogenmethyl groups which are then reacted as described at (l).

(3) By splitting reaction products of a Mannich reaction with aceticanhydride.

(4) By reduction of compounds B carrying aldehyde, ketone or carboxylicacid ester groups in their aromatic rings to the alcohol stage andfurther etherification or esterification, if desired.

(5) By reaction of aromatic metallo-organic compounds with formaldehydeor other aldehydes, or of aromatic aldehydcs the CH0 groups of which areattached to the aromatic nucleus, with metallo-organic compounds.

The preparation of compounds corresponding to the general formula B isknown and described in detail in the literature. Some compounds of thetype B are commercially available. The preparation of the compoundscorresponding to the general formula B does not come Within the scope ofthe present invention.

The compounds of the general formula B may be employed in the form ofmixtures of isomers and/or as mixtures of compounds which differ in theparameter m. It is of advantage, however, as mentioned above, to useuniform compounds of the type B or definitely adjusted mixtures of suchcompounds for condensation, because in this manner the number ofchemical variations in the structure of the condensation products isconsiderably reduced so that reproducible condensation products can beprepared particularly easily. Compounds of the type B are preferred, inwhich the aromatic nuclear positions capable of condensation withcarbonyl compounds or with groups CHR OR or at least some of thesepositions, are occupied by such groups or other groups.

The condensation process according to the invention can also beperformed by using the corresponding thio compounds of the generalformula B However, the condensation process proceeds far less smoothlyin such cases and there may be an annoyance by unpleasant odors.Moreover, these thio compounds of type B are considerably more expensivethan the easily accessible oxygen compounds.

The process of the present invention has a plurality of variationsrelating to the performance of the condensation, the quantitative ratiosemployed and the like.

Condensation in accordance with the invention is performed in thepresence of a strongly acid condensation medium. Preferably employed areconcentrated mod erately strong to strong acids of which the content ofacid predominates with respect to that of diluent. The condensationmedium further should be so selected that it is liquid undercondensation conditions.

The lower limit of the quantity of acid condensation medium which isemployed for the mixed condensations according to all process variationsdescribed is determined by the viscosity of the mixture, and the upperlimit by the economy of the process. The procedure preferably is suchthat, on the one hand, as little acid as possible is used and that, onthe other hand, an easily stirrable and easily mixable condensationmixture is obtained. When selecting the type and quantity of the acid tobe used, the condensability and solubility of the components in the acidshould be considered.

The most favorable conditions for each combination of A(--- D) and B aredetermined in preliminary tests. Particular care should be observed withregard to the exothermic condensation reaction so that it does notproceed too vigorously, since this would impede the control of thereaction procedure and furthermore might lead to decomposition of thediazo compounds.

Exemplary of acids suitable as condensation media are those listed inUS. Pat. No. 3,235,382, column 1, line 71, to column 2, line 5.

Condensation media useful for the present process are phosphoric acid,methanesulfonic acid, and sulfuric acid, which acids are employed inconcentrations of at least 40%, preferably 70 to 100% by weight. Theremainder generally is water, but also may entirely or partially consistof solvents, e.g. methanol, acetic acid, N-methyl-pyrrolidone, and thelike. 85% phosphoric acid, 80% sulfuric acid, and 90% methanesulfonicacid are successfully employed, for example.

80-100%, particularly 85-90%, phosphoric acid is a rather mildcondensation medium in which the condensations can be performed verygently. It is, therefore, the most preferred condensation medium for allcombinations of compounds which will react sufliciently fast under theserather gentle conditions.

80l00%, particularly 90%, methanesulfonic acid is a stronger medium.This acid is advantageous as it dissolves a plurality of components Bstill more readily than phosphoric acid.

Halogen hydracids, such as at least preferably concentrated, aqueoushydrochloric acid or hydrobromic acid, are suitable as condensationmedia only to a limited extent. The use of these acids is lessfavorable, since, under such conditions, halogen alkyl compounds of lowreactivity are formed which do not further react under relativelymoderate condensation conditions.

For the same reason, diazonium salts such as diazonium phosphates orsulfates are superior in many cases to the halides as starting materialsfor condensation.

When diazonium salts are to be used for mixed condensation, which saltsare in the form of the often used metal halide double salts, it isgenerally advisable to dissolve them in the condensation medium, thenpass dry nitrogen or dry air through the mixture until all the chlorideions have escaped in the form of gaseous hydrochloric acid, and then usethe halide-free solution for condensations.

The quantity of the acid serving as the condensation medium may varywithin wide limits. It is possible, for example, to use 1 to 100 partsby weight of acid per part by weight of the mixture of A(D) +B as shownin the examples. The quantity of acid also may be higher withoutgenerally obtaining further advantages, however. It is important toemploy the condensation medium in a quantity sufiicient to ensure aneasily mixable reaction medium.

Depending upon the condensation medium, the cond-ensation partners andtheir concentration in the condensation medium, it may be necessary toaccelerate the condensation reaction by heating or to slow it bycooling. 1t is advisable to use a condensation temperature not in excessof 70 C., since the stability of the diazo compounds A(D) generally islimited at a higher temperature. It is possible, however, to preparediazo condensation products according to the invention also above 70 C.The preferable temperature range for the preparation of the condensatesis from +10 C. to +40 C., however.

It is of advantage to perform all variations of the mixed condensationsin homogeneous reaction media, because reproducible results are mosteasily obtained in such media. Therefore, components B which are notliquid may be employed in the form of solutions, the solvent used beinge.g. methanol, acetic acid and the like. However, if some of thecomponents are only sparingly soluble in the condensation medium, theyalso may be used in the form of very fine suspensions or as emulsions inthe condensation medium. In any case, care should be taken that thecondensation mixture is thoroughly mixed mechanically.

If the condensation process is impeded by an insufficient solubility ofthe starting materials or end products, a homogeneous condensationmedium may be achieved by adding an organic solvent. Of course, testsmust be made in each case to determine which organic solvents aresuitable. Glacial acetic acid has proved to be suitable for many cases,for example. Other suitable solvents are, e.g.: formic acid,N-methyl-pyrrolidone, and methanol. When adding an organic solvent, itshould be considered that this often reduces the efliciency of thecondensation medium, as compared with the unmixed concentrated acid andthat the use of a solvent also may cause side reactions.

For the preparation of the mixed condensates, the pro portions of thereactants A(-D) and B and the conditions of the condensation process maybe varied within wide limits.

It is, in principle, possible to produce mixed conden sates of anydesired composition, e.g. mixed condensates containing only traces of adiazo compound A(D) condensed therein. Generally, mixed condensatescontaining, on the average, 0.01 to 50 moles of second component permole of A(D),,, may be useful for the preparation of valuablelight-sensitive reproduction materials. Apart from special cases, themost important mixed condensates are those which contain 0.1 to 20 molesof second component per mole of A(D) Within this range, the mixedcondensates normally display properties which are clearly distinguishedfrom those of the corresponding homocondensates.

In the simplest and also most preferred case, mixed condensation iseffected by dissolving the A(---D) compound in an acid suitable as thecondensation medium, and adding the compound B either in the form of thesubstance itself or as a solution, while stirring. Various modificationsof this process may be made, bearing in mind, however, that it isdisadvantageous in many cases to dissolve B in the condensation mediumin the absence of A(D) since, depending on the reactivity of Bhomocondensates of B may separate from such solutions more or lessquickly which are no longer easily accessible to a mixed condensation.

However, it is possible in many cases to mix components A(-D) with B andto introduce the mixture or the individual components into the acideither in the form of a solution or as the substances themselves.

In a few cases the condensation reaction may be initiated with the Bcomponent and the A(-D) component may be added later. It is evenpossible, by one of these methods, to condense diazo resins, e.g. thoseprepared by acid condensation of diphenylamine 4 diazonium salts withcarbonyl compounds and having lower condensation degrees, with one orseveral components B in an acid medium. In some cases, a mixedcondensation of a lower molecular weight homocondensate of a secondcomponent B; with A(D) in an acid medium is possible, and even a mixedcondensation of formaldehyde condensates of a compound A(D). withhomocondensates of a compound B or mixed condensates of severalcompounds B in an acid medium may be successfully performed.

In the preparation of soluble condensates generally those components Bare preferred, in which m is 2 or slightly greater than 2, i.e. about 3or 4. Within this class, components with m=2 are particularly preferablesince they yield condensation products of a simpler structure andpolycondensation products carrying more than one diazo group permolecule, when n equals 1 in A(D) and, also when employing several molesof B per mole of A(D) the tendency to formation of cross-linked andsometimes insoluble condensation products is reduced in many cases.Components B in which in is greater than 2 preferably are employed insmaller quantities, the quantity of such compounds generally does notexceed 1 mole per mole of diazo compound.

The upper limit must be ascertained for each individual case byexperiment. An important application of those components in which in isgreater than 2 is their combined use with compounds in which m=2.

Components B in which m=l also may be used for condensation, but in thiscase diazo condensates are obtained which carry only one diazo group permolecule, when 11:1 in A(D) The use of such condensation products in thereproduction layers generally is not preferred. It is of advantage,however, to combine components of type B in which m is 1, with those inwhich "1:2 or a number greater than 2. In these cases, the firstmentioned component B (m=l) may perform the function of a modifier forthe size of the molecules formed during condensation.

The mean molecular weights of the condensation products may vary withinwide limits, depending on the selection of the condensation partners andconditions. It has been found that, for the production of goodreproduction materials, mixed condensates having molecular weightsbetween about 500 and 10,000 are generally preferred. It should beconsidered that these values are mean values and that the molecularweights of the individual constituents of each condensate obtained arestatistically distributed about this mean value. The type ofdistribution is shown in some of the examples below by way of afractionation of the condensates obtained.

The mixtures obtained by condensation can be used directly or furtherprocessed. The mixture also can be worked up and the condensates can beseparated in a solid form.

Working up of the condensation mixtures can be performed in variousways. The method is adapted to the chemical and physical properties ofthe particular reaction product. Mixed condensates containing arelatively large quantity of second component B often can be separatedby stirring the condensation mixture into water. It may occur in thesecases that a more soluble fraction of the mixed condensate can beseparated from the aqueous mother liquor in the form of any sparinglysoluble salt. When the mixed condensate is water-soluble but sparinglysoluble in organic solvents, it is often possible to separate theproduct by diluting the reaction mixture with an organic solvent, e.g.with a lower alcohol or a lower ketone, and the like.

An advantage of many of the condensates prepared according to theprocess of the invention resides in their easy separability in the formof salts free from complex-forming metal salts. Many condensates, forexample, yield sulfates, chlorides, and bromides which are sparinglysoluble in water and can be precipitated from aqueous solutions of thecondensation mixtures by the addition of the corresponding acids ortheir salts soluble in water.

Some separation processes are described in the examples below.

The light-sensitive condensation products preferable are used in theform of diazonium salts. They also can be converted, in known manner,from this form into lightsensitive azides, diazo amino compounds, diazosulfonates, and the like, and, in this form, be used as constituents ofthe reproduction materials of the invention.

Suitable components A(D) and B for the preparation of the condensationproducts of the invention are,

principally, all compounds which are capable of condensation in an acidmedium and the basic structures of which are not decomposed under thecondensation conditions.

As a rule, all compounds B are capable of condensation in an acid mediumaccording to the process of this invention, the basic structures ofwhich are themselves capable of reaction with formaldehyde in suchcondensation medium.

Groups effecting the condensability of the compounds A(---D) and EH(which is the basic structure from which 13 is derived) are thefollowing:

(1) Aryl radicals and heterocyclic radicals which have nuclear positionscapable of condensation. Preferred are radicals in which these nuclearpositions are activated. This activation may be effected, for example,by annealation with additional aromatic rings or by substitution bygroups such as OH, O-alkyl, O-aryl, SH, S-alkyl, S-aryl, alkyl, aryl,amino, alkylamino, dialkylamino, -arylamino, diarylamino, and the like.In addition to these activating substituents, the condensable aromaticor heterocyclic radicals also may contain condensation-inhibitinggroups, e.g. nitro or sulfonic acid groups, if the activation caused byother groups is only reduced but not eliminated.

(2) Radicals which themselves are capable of condensation and may bedirectly linked to isoor heterocyclic radicals or to aliphatic radicalsor, if desired, may be directly linked to one another. Such radicals aregroups such as carboxylic acid amide, sulfonic acid amide,N-alkylsulfonic acid amide, N-arylsulfonic acid amide, nitrile, urea,thiourea, urethane, ureido, thioureido, glyoxaldiureine, imidazolone,guanidine, dicyanodiamide, and amino groups directly attached toaromatic rings.

The following compound types or individual compounds are illustrative ofthe components of general formulae A(-D) and B which are used for thepreparation of the diazo condensation products of the invention.

Diazonium compounds A(D) .-The basic idea is that a benzene nucleuscarrying the diazo group, apart from only few exceptions (e.g.4-diazophenol) not included here, is deactivated to such an extent thatcondensation in nuclear positions of this ring is no longer possibleunder less severe conditions.

The diazonium compounds to be used in accordance with the presentinvention thus contain in the radical A, in addition to the aromaticisoor heterocyclic nucleus carrying the diazo group, at least onearomatic isoand/ or heterocyclic ring having at least one condensablenuclear position and/or substituents of the above Type 2, which arethemselves capable of condensation.

An important group of diazonium compounds particularly for processinginto condensation products in accordance with the present invention hasa structure according to the following general formula in which p is aninteger from 1 to about 3, preferably 1;

X is the anion of the diazonium salt; it also may be formed by an acidsubstituent of the molecule;

R is an aromatic isoor aromatic heterocyclic group, if

desired substituted, which has at least one position capable ofcondensation, and preferably is a phenyl group, if desired substituted.

Preferable substituents are those which increase the reactivity of thenucleus with respect to condensation, e.g. the alkyl, alkoxy,alkylmercapto, aryloxy, arylmercapto, hydroxy, mercapto, amino, andanilino groups.

R is an aromatic ring of the benzene or naphthalene series, which, inaddition to the diazo group, may carry other substituents;

R is a connecting member between the rings R and R e.g. of the followingtypes, of which the radical R is always to be considered on theleft-hand side, and the .13. group R on the right-hand side, if R is notsymmetrical:

Simple homopolar bond (C-H NR (q is a number from to 5, R is H, or alkylwith 1 to carbon atoms, or aralkyl with 7 to 12 carbon atoms or arylwith 6 to 12 carbon atoms) -(CH NR --(CH NR (r is a number from 2 to 5,R is H or alkyl with 1 to 5 carbon atoms) --OR -O-- (R is arylene with 6to 12 carbon atoms) Exemplary of compounds of the formula2,3',S-trimethoxy-diphenyl-4-diazoniumchloride2,4,S-triethoxy-diphenyl-4-diazoniumchloride 4- 3-( S-methoxy-phenyl)-propylamino] benzenediazoniumsulfate4-[N-ethyl-N-(4-methoxy-benzyl)-amino]- benzenediazoniumchloride 4- [N-(naphthyl- (2) -methyl-N-n-propyl-amino] benzenediazoniumsulfate 4-N-3-phenoxy-propyl) -N-methyl-amino] -2,5-dimethoxy-benzenediazoniumtetrafluoroborate 4- [N(3-phenylmercapto-propyl-Nethylamino] -2-chloro-S-methoxy-benzenediazoniumchloride 4- [4- (3-methyl-phenoxy)-phenoxy] -2,5-dimethoxybenzenediazoniumchloride 4-4-methoxy-phenylmercapto) -2,5-diethoxybenzenediazoniumchloride 4- (3 ,5-dimethoxy-b enzylamino -2,5-diethoxybenzenediazoniumhexafluorophosphatecarbazole-3-diazoniumchloride3-methoxy-diphenyleneoxide-2-diazoniumchloridediphenylamino-4-diazoniumsulfatc 2,5-diethoxy-4-phenoxy-benzene-diazoniumchloride Mixed condensatesparticularly suitable for use in the reproduction layers of thisinvention are obtained by using diazo compounds of the general formula pis an integer from 1 to 3, preferably 1,

R is a phenyl group either unsubstituted or substituted by one or morealkyl or alkoxy groups,

R is a benzene ring which, in addition to the diazonium group, may carryone or two identical or difierent substituents which may be halogenatoms, alkyl groups with 1 to 4 carbon atoms, or alkoxy groups with 1 to5 carbon atoms, and

R is a homopolar bond or one of the members A particularly importantgroup of diazo compounds having structures according to the generalformula R R R -N X, and which are preferably used in accordance with thepresent invention for the preparation of the diazo condensationproducts, are the salts of the diphenylamine-4-diazonium ion and itssubstitution products since these are particularly easily condensable inmany cases and the condensation products yield particularly valuablereproduction layers.

Preferably employed substituents which may be linked to the phenylnuclei of the diphenylamine-4- diazonium compounds are alkyl and alkoxygroups with l to 6, preferably l to 2, carbon atoms, furthermore thehalogens and the following groups -COOR (R is H, alkyl or aryl) -COR (Ris alkyl or aryl) SO OR (R is H, alkyl or aryl) NHCOR (R is alkyl oraryl) -NHR and NRR' (R and R are alkyl, aryl, aralkyl) Exemplary of suchsubstituents which may be linked to the phenyl nuclei of thediphenyldiazonium group are methyl, propyl, isobutyl, trifluoromethyl,methoXy, difluoromethoxy, ethoxy, hydroxyethoxy, ethoxyethoxy, fluorine,chlorine, bromine, iodine, ethoxycarbonyl, phenoxycarbonyl, acetyl,methoxysulfonyl, ethoxysulfonyl, acetylamino, methylamino, ethylamino,dimethylamino, diethylamino, methylethylamino, phenylamino, benzylamino,methylbenzylamino, and ethylbenzylamino.

Suitable diphenylamine-4-diazonium salts are, for example, the diazoniumsalts derived from the following amines:

4-amino-diphenylamine, 4-amino-3-methoxy-diphenylamine,4-amino-2-methoxy-diphenylamine, 4'amino-2-methoxydiphenylamine,4-amino-4-methoxy-diphenylamine, 4-amino-3-methyl-diphenylamine,4-amino-3ethyl-diphenylamine, 4'-amino-3-methyl-diphenylamine,4-amino-4-methyldiphenylamine, 4-amino-3-ethoxy-diphenylamine,4-amino-3-hexyloxy-diphenylamine,4-amino-3-hydroxy-ethoXy-diphenylamine,4'-amino-Z-methoxy-S-methyl-diphenylamine,4-amino-3-methoxy-d-methyl-diphenylamine, 4'-amino3,3-dimethyl-diphenylamine, 3'-chloro-4-amino-diphenylamine,4-amino-4-n-butoxy-diphenylamine, 4-amino-3,4-dimethoxy-diphenylamine,4-amino-diphenylamine-2-sulfonic acid,4-amino-diphenylamine-2-carboxylic acid,4-amino-diphenylamine-2-carboxylic acid, and4-bromo-4-amino-diphenylamine.

Preferably employed are 4-amino-diphenylamine and3-methyl-4-amino-diphenylamine, particularly preferable are the3-alkoxy-4-amino-diphenylamines having 1 to 3 carbon atoms in the alkoxygroup, especially the 3- methoxy-4-amino-diphenylamine.

Diazonium compounds A(D) useful in the condensation reaction inaccordance with the invention also may be homocondensation products ofthe described diazo compounds with active carbonyl compounds, i.e.relatively low-molecular weight types of the known diazo resins, forexample, which, in accordance with the invention, can be regarded aslarger molecules capable of further condensation and having severaldiazo groups.

The diazonium compounds A(D) may be reacted in the form of any solublesalt of a moderately strong to strong acid, e.g. in the form of a saltof sulfuric acid, orthophosphoric acid, hydrochloric acid,trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, andthe like. Preferably employed are the sulfates and the phosphates.

Components B Similarly, a plurality of compounds are suitable ascomponents B in the preparation of the mixed condensates. An importantclass are those derived from the substituted or unsubstituted aromatichydrocarbons and aromatic heterocyclic compounds provided the basiccompounds have nuclear positions capable of condensation, in an acidmedium, with carbonyl compounds and, accordingly, of receiving the CHROR groups.

A large number of unsubstituted aromatic isocyclic and heterocycliccompounds are thus suitable as basic compounds EH for the components Be.g. benzene, naphthalene, anthracene, phcnanthrene, pyrene, indene,fluorcne, acenaphthene, thiophene, furane, benzofurane, diphenyleneoxide, benzothiophene, acridine, carbazole, phenothiazine, and the like.These aromatic compounds may contain one or more identical or difierentsubstituents.

Exemplary of such substituents are:

wherein R may be H, COalkyl, CO-aryl, CO-heteroyl,

-CO-aralkyl, SO alkyl, SO aryl,

SO aralkyl,

SO heteroyl, CONH CSNH CONHalkyl,

The meanings of certain expressions are as follows:

Alkyl: A branched or unbranched alkyl group with l to 10 carbon atomswhich may be substituted, e.g. by halogen, alkoxy, OH, COOH, CONH CN,COCH SO H, or PO H or hydrogens in neighbouring positions may bereplaced by oxygen (epoxides) or removed (multiple bonds). The alkylradical also may be interrupted, e.g. by O, S, -N(alkyl), SO or SO.

Aryl: A monoor polynuclear aromatic ring which, including alkyl, alkoxyor aralkyl groups which may be linked to it, contains 6 to carbon atoms.The aryl nucleus may carry additional substituents.

Aralkyl: A group containing 7 to 20 carbon atoms which is composed ofalkyl and aryl radicals (corresponding to the above definition).

Alkoxy: O-alkyl group, the alkyl having the above meaning.

The alkyl, aryl, aralkyl, and alkoxy groups may be present once orseveral times, either alone or together. For not exceeding the portionof these substituents with respect to the molecular Weight of B theportion of the four above-described substituents is limited in compoundEH with respect to the structure of the molecule, the primarily givenaromatic isoor heterocyclic ring or the condensed ring system is to besubstituted only to such an extent that, in the case of substitution,this compound is increased by alkyl groups: only by a maximum of 10carbon atoms by aryl groups: only by a maximum of 20 carbon atoms byaralkyl groups: only by a maximum of 10 carbon atoms, and

by aralkyl groups: only by a maximum of 20 carbon atoms.

The total increase in C atoms by means of these four types ofsubstituents together should not exceed C atoms with respect to theoriginal aromatic nucleus.

It results therefrom that substituents of longer chains, i.e. thosewhich have a relatively large number of C atoms, occur less frequentlytogether than those with few C atoms. Generally, the short-chain alkyland alkoxy groups (1 to 4 carbon atoms) and the smaller aromaticradicals are preferred in aryl and aralkyl groups (up to 12 C atoms)since the corresponding compounds are more easily soluble in thecondensation media and condensation thus can be performed more easily.Limitation 16 of substitution, as described above, results from the samereason.

The condensable isoor heterocyclic aromatic rings also may havesubstituents exerting a deactivating effect on the nuclei, e.g. O N,HOOC, NC-, HO S, H O P--, Cl, Br, and the like, provided condensabilityis not eliminated thereby. This will particularly be the case when thering as such is easily condensable or when it carries substituentshaving a considerable activating effect. Another possibility forintroducing deactivating substituents without reducing thecondensability of the ring is to place the substituents in side-chains,e.g. aliphatic side-chains.

substituents deactivating nuclear condensation also may be present inthose cases in which the reactivity of the condensable nucleus is notnecessary because the nucleus has substituents at which condensation cantake place. Such substituents have been listed above, for example thegroups CO-NH SO NH andSO NH- alkyl.

According to the above, the basic compounds EH or the components Bderived therefrom belong to the following groups of substances, forexample:

aromatic compounds (isoand heterocyclic) unsubstituted or substitutedaromatic amines phenols and thiophenols phenolethers andthiophenolethers urea, thiourea, carboxylic acid amides (aliphatic andaromatic), and

sulfonic acid amides (aliphatic and aromatic).

Exemplary individual representatives are listed below.

Soluble types of the new diazo condensation products preferably are usedin this invention. In addition to a corresponding selection of thecomponents A(D) and B according to their properties and their ratiosthere are preferably further used, for promoting the formation ofsoluble condensation products, components B the basic structures EH ofwhich have molecular weights (amines are regarded as free amines, not inthe form of salts: acid groups are considered in the H form) less than500, preferably less than 250. In the case of aromatic compounds, thosecompounds are preferred within these which do not contain more than 4,preferably 1 to 2, especially 2, aromatic single rings (anneallatedand/or preferably linked via homopolar bonds and/or via intermediatemembers).

The use of the compounds B of the lower molecular weight range isadvantageous also because often they are more readily soluble in thecondensation medium and thus can react more easily.

Of the indicated classes of compounds from which the compounds B derive,generally those are preferred which are unsaponifiable or onlydifficultly saponifiable under acid condensation conditions. The sameapplies to the diazo compounds A(D) For this reason, those basiccompounds for the components belonging to the series of the aromaticisoand heterocyclic compounds are advantageous which are unsubstitutedor carry as substituents the groups alkyl, aralkyl, aryl, alkoxy,alkylmercapto, aryloxy, arylmercapto, OH, SH, and amino, if desired inaddition to unsaponifiable deactivating substituents, e.g. COOH. Ofthese compounds, those aromatic isoand heterocyclic compounds areparticularly preferred which are unsubstituted and/ or contain assubstituents one or more of the radicals alkyl, aralkyl, aryl, alkoxy,alkylmercapto, arylmercapto, and aryloxy, particularly when condensatesare desired which should not contain salt-forming groups other than thediazo group.

Exemplary of particularly suitable types of compounds B are thosederived from diphenylether, diphenylsulfide, diphenylmethane andbiphenyl which may contain one or two substituents selected from thegroup consisting of 1 7 halogen atoms, alkyl groups, and alkoxy groups,however which are preferably unsubstituted.

If these compounds are condensed with diphenylamine- 4-diazonium saltswhich are unsubstituted or substituted by a lower alkyl group or a loweralkoxy group containing up to 3 carbon atoms, mixed condensates areobtained in a very smooth reaction, which can be precipitated veryreadily in good yields in the form of salts of hydrochloric acid, ofhydrobromic acid, or of suitable sulfonic acids mentioned below,especially when the component B is employed in proportion of 0.5 to 2moles per mole of diazo compound.

The new condensation products of the invention generally contain 0.01 to50 moles, preferably 0.1 to 20 moles, on the average, of units ofcomponent B per mole of units of component A(D) A particularly preferredrange is from 0.2 to 2 moles of B per mole of A(--D) The use of thecondensates may be effected in various ways. In some cases, the newcondensation products may be employed in the form of crude condensates,i.e. without separating the condensation medium. This is especiallypossible, when the quantity of condensation medium per mole of diazocompound can be maintained small.

Generally, the new condensation products are separated in the form ofany salt and in this form, after the addition of any desired additionallayer constituents, are used for the production of the reproductionmaterial.

The diazo condensation products may be separated as salts of thefollowing acids and then be employed: hydrohalogenic acids, such ashydrofluoric acid, hydrochloric acid, and hydrobromic acid; sulfuricacid; nitric acid; phosphoric acids (S-valent phosphorus), particularlyorthophosphoric acid; in organic isoand heteropolyacids, e.g.phosphotungstic acid, phosphomolybdic acid; aliphatic or aromaticphosphonic acids or their semiesters; arsonic acids; phosphinic acids;trifiuoroacetic acid; amidosulfonic acid; selenic acid; fluoboric acid;hexafluorophosphoric acid, and perchloric acid; furthermore aliphaticand aromatic sulfonic acids, eg methanesulfonic acid, benzenesultonicacid, toluenesulfonic acid, mesitylenesulfonic acid,p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid,sulfosalicylic acid, naphtha- 1ene-1-sulfonic acid,naphthalene-2-sulfonic acid, 2,6-ditert.-butyl naphthalenesulfonic acid,2,6-di-tert.-butylnaphthalenedisulfonic acid,l,8-dinitronaphthalene-3,6- disulfonic acid,4,4'-diazidostilbene-3,3-disulfonic acid, Z-diazo-l-naphthol-4-sulfonicacid, 2-diazo-1-naphthol-5- sulfonic acid, 1-diazo-2-naphthol-4-sulfonicacid, and the like. Other organic sulfonic acids suitable for theseparation of the condensates are listed in columns 2 to 5 of U.S. Pat.No. 3,219,447.

The new diazo condensation products also can be separated in the form ofthe double salts with metal halides or pseudo halides, eg of the metalszinc, cadmium, cobalt, tin, and iron, or as the reaction products withsodium tetraphenyl borate or with 2-nitroindanedione-(1,3), and then beused in known manner.

-By the action of sodium sulfite, sodium azide or amines, they also canbe converted into the corresponding diazosulf'onates, azides ordiazoamino compounds and be employed in this form, as is known in thecase of the diazo resins.

The following advantages of the new diazo condensation products havebeen indicated before:

(a) Minor penetration of the diazo compound into supports favoring thisphenomenon, e.g. superficially saponified cellulose acetate film. Theresult is that the image areas have excellent oleophilic propertiesafter exposure to light.

(b) Minor sensitivity of the reproduction layers to fingerprints.

B'oth advantages generally become more and more noticeable with theincrease of the proportion of incorporated component. Whereas theadvantage becomes gen- 18 erally apparent in case (a) with condensatescontaining as little as 0.1 mole of B per mole of A(D) the desiredeffect is obtained in case "(b) only from about 0.5 mole, in some casesonly at a higher degree of incorporation of these components.

The use of the new condensation products has other advantages inaddition to those indicated above. Oompared with the known diazo resins,an improved eifective light-sensitivity of the reproduction layersprepared with the new condensation products can be observed, i.e. whenusing the same light source, shorter exposure times are required. Also,this eifect generally increases with an increase of the content of B anddiiters, depending upon the type of component B selected. The effectgenerally is the more the higher the molecular weight of component BGenerally, an increase of the components by another aromatic ring has agreater effect than the same increase of the molecular weight by othergroups.

With an increasing content of a suitable second component B the resincharacter of the mixed condensates becomes increasingly more pronounced,while the salt character decreases with the decreasing content ofdiazonium salt groups in the molecule of the condensate. Consequently,such mixed condensates are more compatible with polymerisates which donot contain ionizable groups.

For the same reason, the mixed condensates often possess goodfilm-forming properties and the films show in the fully exposed state animproved flexibility and in many cases a good resistance to variousetching agents. Thus, is is possible with a number of mixed condensatesto produce reproduction layers of satisfactory etching resistancewithout the customary addition of resins, which layers may be used, e.g.for the photomechanical preparation of halftone gr-avure plates, printedcircuits etc.

Mixed condensates are particularly suitable for this purpose whichcontain components that are not capable of forming a salt with acid oralkaline etching agents and have no tendency for hydrolytic splitting,i.e. second components selected from the group of aromatic hydrocarbons,either unsubstituted or substituted by alkyl, alkoxy, alkylmercapto,aryloxy or arylmercapto groups.

-A particularly favorable group of condensation products is derived fromcomponents B containing 2 benzene rings linked via a bridge member.

Particularly preferred in this series are the mixed condensates fromcomponents B; which are derived from diphenylether, diphenylsulfide,diphenylmethane or biphenyl with diphenylamine-4-diazonium salts,particularly 3- alkoxy-diphenylamine-4-diazonium salts. These condensates have a high light-sensitivity and those made from 3-alkoxy-diphenylamine-4-diazonium salts have simultaneously a surprisinghigh storability. The corresponding condensation products can beprepared particularly easily and under moderate conditions.Diphenylether derivatives of Type B suitable for the preparation of thecondensation products are commercially available.

In contradistinction to the known diazo resins, the new condensationproducts, can be separated in many cases very easily from an aqueoussolution by the addition of hydrochloric acid or common salt solution inthe form of the chlorides or analogously as bromides. For this reason, anumber of the new condensation products can be advantageously employedin those cases where the halides of the known diazo resins, which can beseparated in a cumbersome manner only, have been preferably employed,e.g. for the production of screen printing forms. Furthermore, thechlorides can be easily converted into the salts of acids of lowvolatility, e.g. into the orthophosphates, which, of course, also may beobtained directly, e.g. by condensation of the diazonium phosphates inphosphoric acid.

A special group of the new condensation products has particularadvantages with respect to the acid resistance of the exposure productsand their adhesion to metallic sup ports. These are the condensationproducts carrying phos-' phonic acid groups. The exposure products ofthese condensates have good adhesive properties on aluminum foilsroughened by metal brushes only, for example, without the foils beingprovided with one of the known chemical adhesive layers, and even thenwhen the products are employed in the form of the zinc chloride doublesalts.

Another special group of mixed condensates has special advantagesparticularly for the hardening of hydrophilic colloids. Mixedcondensates belonging thereto are mixed condensates ofdiphenylamine-4-diazonium salts and urea or similar compounds. Colloidlayers which are hardened with these condensates with the action oflight, have better hydrophilic properties after hardening than havethose sensitized with the hitherto known diazo resins. This effect isimportant for the production of printing forms as described in U.S. Pat.No. 3,085,008, for example.

It also should be noted that mixed condensates prepared from diazoniumsalts and an excess of phenols are capable of yielding positive copiesupon aqueous alkaline development (if desired with the addition of asmall quantity of solvent).

The new condensation products can be combined with water-soluble andwater-inosoluble polymers in the reproduction materials of theinvention. Particularly, the production of reproduction layerscontaining water-insoluble polymers is simplified when using the newcondensation products, since the latter can be particularly easilyobtained in the form of salts compatible with these polymers, which arereadily soluble in a number of organic solvents.

The reproduction layer is prepared in a manner analogous to that in thecase of the known diazo resins, i.e. the diazo condensates are dissolvedas such or, if desired, together with additional layer constituents in asuitable solvent and a support is coated with the solution thusobtained. Suitable supports are, e.g. those mentioned in C01. 2 of thepresent specification.

In some cases, it is also possible to apply the mixed condensates in theform of a very fine suspension. Coating may be performed, for example,by immersing or casting and draining, by casting and whirling off theexcess solution, by brushing, swabbing or by roller application, as wellas by other coating methods. The coating is then dried at roomtemperature or at an elevated temperature.

A number of substances may be added, as other constituents, to thereproduction layers. Exemplary thereof are:

Acids, e.g. phosphoric acids (particularly those of the 5-valentphosphorus, preferably orthophosphoric acid), phosphonic acids,phosphinic acids, and arsonic acids, furthermore the strong acidsdescribed in U.S. Pat. No. 3,235,382, such as sulfuric acid, hydrobromicacid, organic sulfonic acids, e.g. toluenesulfonic acid, methanesulfonicacid, and naphthalene-1,5-disulfonic acid, furthermore arsenic acid, andhexafluorophosphoric acid, furthermore the organic polyacids describedin U.S. Pat. No. 3,179,518, e.g. polyacrylic acid, polyvinylphosphonicacid, polyvinylsulfonic acid, mellitic acid, andpolyvinylhydrogenphthalate.

Water-soluble polymers, e.g. polyvinyl alcohol, polyethylene oxide,partially saponified polyvinyl acetate with an acetyl content up toabout 40 per cent, polyacrylamide, polydimethylacrylamide,polyvinylpyrrolidone, polyvinyl methyl formamide, polyvinyl methylacetamide and copolymers of monomers forming these polymers or withmonomers which alone form water-insoluble polymers, in such a quantitythat the water-solubility of the copolymers is maintained, furthermorenatural substances or modified natural substances, such as gelatine,methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulosealginates, and the like.

Polymers sparingly soluble or insoluble in water, e.g. phenol resins,epoxy resins, oil-modified alkyd resins, amineformaldehyde resins, suchas urea and melamine resins, polyamides, polyurethanes, polyvinylresins, polyacrylic and polymethacrylic acid esters, polyvinyl acetals,polyvinylchloride, polyesters, and polyethers, as obtained, for example,by the polymerization of vinyl ethers, of oxiranes, oxetanes ortetrahydrofuran. The polymers also may carry groups capable of enhancingsolubility in alkali, e.g. carboxyl, carboxylic acid anhydride, sulfonicacid, sulfonic acid amide, and phosphonic acid groups, furthermoresulfuric acid semi-ester, phosphoric acid mouoester and phosphonic acidmouoester groups. The polymers may be incorporated into the reproductionlayers either individually or, when they are compatible with oneanother, also in the form of mixtures.

Printing forms of substantially increased length of run are obtainedfrom reproduction layers containing the mixed condensates in combinationwith polyvinyl formal resins, particularly on grained aluminum supports:

Colored or uncolored pigments Dyestuffs Plasticizers Wetting agentsSensitizers Indicators Fatty acids Aldehydes, particularly formaldehyde,also may be added to the reproduction layers.

All additives should be so selected, of course, that they are compatiblewith the diazo condensates and, furthermore, absorb light to as low adegree as possible in the Wave length range important forlight-decomposition of the diazo compounds.

The additives generally may be incorporated into the reproduction layersin the following quantities:

Acids: On metal supports and superficially saponified cellulose acetatefilms, acids of 5-valent phosphorus, particularly orthophosphoric acid,generally are employed in quantities of 0.01 to 4 moles, phosphonic andarsonic acids in quantities of 0.01 to 3 moles, per mole of diazogroups. On paper supports as described in U.S. Pat. No. 2,778,735, inaddition to phosphoric acid, there also may be used strong acids, e.g.those described above, in quantities of l to 100 moles at the most permole of diazo groups. In this connection, 1 mole means the quantitywhich contains 1 gram-atom P, As or an equivalent COOH.

The organic polyacids, insofar as they are readily water-soluble,generally are used in quantities of only 0.01 to 3 moles per mole ofdiazo groups.

The water-soluble polymers generally are used in quantities up to 100parts by weight per part by weight of diazo compound, preferably notmore than 20 parts by weight.

The addition of polymers insoluble in water generally will not exceed 20parts by weight per part by weight of diazo compound; the preferredrange is not more than about 10 parts by weight.

When the reproduction layers contain water-soluble and/orwater-insoluble polymers, colored or uncolored pigments generally areadded to them only in quantities not exceeding 50 percent by weight,calculated on the Weight of the polymers.

Plasticizers, dyestuffs, wetting agents, sensitizers, indicators, andfatty acids generally are incorporated into the reproduction layers inquantities not exceeding 20 percent by weight, preferably not exceeding10 percent by Weight, calculated on the weight of the other layerconstituents.

Reproduction layers containing or consisting of the new diazocondensates also may be combined with known light sensitive systems.This applies, for example, to the known diazo resins (formaldehydecondensates of the substituted or unsubstituted 4-diazo-diphenylamine),p-quinonediazides, iminoquinonediazides, azido compounds,photo-crosslinkable polymers with azido groups,

chalcone groupings, cinnamic acid groupings, allyl ester and allyl ethergroups, and to photopolymer layers.

Depending upon the layer constituents, suitable solvents for thepreparation of the coating solutions are, for example, water, alcoholssuch as methanol, ethanol, and ethylene glycol monoethyl ether, dimethylformamide, diethyl formarnide, and the like. Water, if desired with theaddition of an organic solvent, is preferably employed in the case ofmetal halide double salts, sulfates, and phosphates of the new diazocondensates.

Pure organic solvents or those containing only a little water arepreferred in the case of chlorides, bromides, and salts of the new diazocondensates, which are waterinsoluble to a large extent, e.g. the saltsof organic sulfonic acids, fluoboric acid, and hexafiuorophosphoricacid. In these cases, to the alcohols or amides Which normally are goodsolvents for these compounds, there are added solvents which dissolvethem only sparingly, e.g. ethers such as dioxane, and tetrahydrofuran:esters such as acetic acid ethyl ester, butyl acetate, and ethyleneglycol monomethyl ether acetate: ketones such as methyl ethyl ketone,cyclohexanone, and the like, in order to improve the levellingproperties of the coating compositions.

The reproduction materials thus produced may be used directly afterproduction, but there also may be days, weeks or months betweenproduction and processing. It is advantageous to store them at a cool,dry place.

The reproduction material is processed by image-wise exposure through anoriginal. For image-wise exposure to light, any light source,conventional for reproduction purposes, may be used which emits in thelong-wave ultraviolet range and in the short-wave visible range, e.g.carbon are lamps, high-pressure mercury vapor lamps, xenon impulselamps, and others.

After exposure to light, development is effected with a suitabledeveloper. Suitable developers are, for example, water, mixtures ofwater with organic solvents, aqueous salt solutions, aqueous solutionsof acids, e.g. of phosphoric acid, to which salts or organic solventsmay be added, or alkaline developers, e.g. aqueous solutions of sodiumsalts of phosphoric acid or silicic acid. Also organic solvents may beadded to these developers. In some cases, it is also possible to developwith undiluted organic solvents. The developers may contain additionalconstituents, e.g. wetting agents, and hydrophilizing agents.

Development is performed in known manner, e.g. by immersing or wipingover or rinsing with the developer liquid.

The reproduction layers prepared with the new diazo condensationproducts yield negative copies of the originals employed in nearly allcases. When adding phenol resins to the reproduction layers,particularly in excess of the mixed condensate, positive copies of theoriginal are obtained, however, with alkaline development.

Depending upon the composition of the layer, the supporting material,and processing, it is possible to produce with the new diazocondensates, for example, single copies, relief images, tanned images,printing forms for screen printing, relief printing, intaglio printing,and planographic printing, or printed circuits. In many cases, it ispossible to improve the abrasion resistance and the chemical resistanceof the image stencil by burning in.

The reproduction materials according to the invention can be stored formonths, provided suitable components have been selected. Alternatively,the reproduction layers may be applied to a support immediatelypreceding use, if this is desirable. The mixed condensates according tothe invention are very suitable for use in socalled wipe-on processes,in which a support, particularly an aluminum support, which has beenmechanically and/or chemically pretreated in an appropriate manner, iscoated either manually or with the aid of simple devices with alight-sensitive layer by the printer for the photomechanical preparationof a printing plate. For this purpose, the high light-sensitivity of thediazo compounds and the excellent oleophilic properties of theirlight-decomposition products are also of particular advantage.

The novel diazo mixed condensates may also be used by the printer forsensitizing pre-coated (but not presensitized) screen printing fabrics.Alternatively, they may be used for the preparation of pre-sensitizedscreen printing stencils, which have the advantage over knownchromate-sensitized screen printing stencils that they possess aconsiderably better storability. The good lightsensitivity of the noveldiazo compounds is also of advantage for screen printing.

The invention is further illustrated by the following series of compoundtypes and individual compounds, which are suitable as components B forthe preparation of the condensation products to be employed inaccordance with the present invention.

The preparation of compounds of the general formula B is known anddescribed in detail in the literature. Some of the compounds of Type Bare commercially available.

Condensation products with the use of such components B alone or withothers also can be used for the production of reproduction materials.

The compounds of the general formula B may be employed as isomermixtures and/ or as mixtures of compounds B which diifer in theparameter m. It is often of advantage to employ uniform compounds ofType B or particularly adjusted mixtures of such compounds forcondensation, since chemical variation in the struc ture of thecondensation products is substantially reduced thereby and areproducible production of the condensation products is facilitated.

The following list of components B represents a classification. Thecharacteristic feature in each case is the substituent activatingcondensation. When two or more diiferent activating substituents occur,attribution to a certain group is at random, of course.

In some cases, it is possible to employ also aromatic compoundssubstituted only by deactivating substituents as the basic compounds forcomponents B Examples thereof are in the first group of the followinglist.

Preferably employed, however, are compounds listed in the followinggroups, i.e. compounds of Type B carrying activating substituents or nofurther substituents except the CHR OR groups.

Compounds B Derived From Aromatic Isocyclic and Hetero-Cyclic CompoundsBenzylalcohol Dibenzylether 1,3-Bis-hydroxymethyl-benzene1,4-Bis-methoxymethyl-benzene 1,5-Bis-acetoxymethyl-naphthalene1,4-Bis-hydroxymethyl-naphthalene 1-Hydroxymethyl-naphthaleneZ-Hydroxymethyl-naphthalene 9,10-Bis-methoxymethyl-anthracene9-Hydroxymethyl-phenanthrene 2,S-Bis-methoxymethyl-thiopheneZ-Hydroxymethyl-furan Bis-methoxymethyl-diphenyleneoxideBis-methoxymethyl-diphenylenesulfideBis-methoxymethyl-dimethyldiphenyleneoxide2,6-Bis-hydroxymethyl-naphthalene Benzhydrol 1,4-Bis- (a-hydroxybenzyl)-benzene 3-Methyl-hydroxymethyl-benzene2,5-Dimethyl-hydroxymethyl-benzene2-Methyl-5-isopropyl-hydroxymethyl-benzene4,6-Dimethyl-1,3-bis-hydroxymethyl-benzene 23 2,5-Dimethyl-1,4-hydroxymethyl-bcnzene2,4,6-Trimethyl-1,3-bis-hydroxymethyl-benzene 2,4,6-Trimethyl- 1,3,5-tris-methoxymethyl-benzene 2,3,5,6-Tetrarnethyl-1,4-bis-acetoxymethyl-benzene 2,4,5 ,6-Tetramethyl-1,3-bis-ethoxymethyl-benzene 4,4'-Bis-acetoxymethyl-diphenylmethane 4,4-Bis-methoxymethyl-diphenyl Z-Methyl-l,S-bis-acetoxymethyl-naphthalene2-Ethyl-9,10-bis-methoxymethyl-anthracene2,4-Diisopropyl-hydroxyrnethyl-benzene4,6-Diisopropyl-1,3-bis-hydroxymcthyl-benzene 4,6-Diisopropyll,3-bis-methoxymethyl-benzene 6-Chloro- 1-hydroxymethyl-naphthalene4,4-Bis-acetoxymethyl-dihpenylsulfone 4,4-Bis-methoxymethyl-benzophenone4-Chloro-hydroxymethyl-benzene Well defined derivatives of type B; ofaromatic amines can not be obtained as easily as in the case of othercompound types, since, inter alia, they have a marked tendency to splitoff water, and since a number of by-reactions are possible. Examples ofsuch products obtained by splitting-01f water areN,N-methylene-bis-diphenylamine and anhydro-formaldehyde-aniline. Thesecompounds also are capable of condensation in an acid medium accordingto the process of the invention.

Compounds B derived from phenols, i.e. from compounds in which the OHgroup is linked directly to an isoor heterocyclic aromatic ring systemand which may include one or more aromatic rings. These rings may carryany further substituents with the condition that at least one positionwhich may carry a group -CHR OR is maintained in the molecule.

wherein R is a monovalent radical and from to 4.

Examples of combinations of R and s:

s is a number R 3 Isomers Alkyl (1 to 3 carbon atoms) 1-4 All. Alkyl (4to carbon atoms)... 1-2 All. Halogen (F, Cl, Br, I) 1-2 All. Aralkyl, ifdesired substituted (7 to 12 All.

carbon atoms). Aryl, if desired substituted (6 to 20 carbon 1-2 All.

toms Alkoxy and alkymercapto (1 to 3 carbon 1-3 All.

atoms). Alkoxy, alkylmercapto and aralkoxy, it 1-2 All.

desired substituted (4 to 10 carbon atoms). Aryloxy, arylmcrcapto, ifdesired sub- 1-2 All.

stituted (6 to 20 carbon atoms). Alkylamino, dialkylarnino (1 to 4carbon 1-2 All.

atoms). Arylamino (6 to 10 carbon atoms) 1-2 All. Aryl-SOz', (6 to 14carbon atoms) 1 Preferably in para-position to the OH group. S0311,POaHz, AsOaHz, COOH and the Do.

corresponding esters and amides.

The phenol alcohols B obtained from the above-mentioned phenols by meansof formaldehyde addition as well as the ethers and esters thereof at thealiphatic OH .group can be used in the process of the invention.Numerous phenol alcohols are described in the literature. A summary canbe found, for example, in the monograph of Martin The Chemistry ofPhenolic Resins, John Wiley & Sons, N.Y., 1956. Also, the periodical DieMakromolekulare Chemie, 44, pages 44 to 45 (1961) should be noted. Alsosuitable are phenol alcohols and the esters and ethers thereof, whichare obtained in another manner, e.g. by halogen methylation or reductionof phenol aldehydes or phenol carboxylic acids or the esters thereof.

In addition to the phenol alcohols and their abovementioned derivatives,it is also possible to employ the 24 derivatives obtained byesterification of the phenolic OH group of these compounds by means ofcarboxylic and sulfonic acids.

The following phenol alcohols and derivatives thereof are suitable, forexample:

2-Hydroxy-hydroxymethyl-benzene6-Hydroxy-2,4-dimethyl-1,3,S-tris-hydroxymethyl-benzene6-Acetoxy-3-methyl- 1,5 -bis-acetoxymethyl-benzene5-Chloro-2-hydroxy1,3-bis-hydroxymethyl-benzene5-tert.-Butyl-2-hydroxy-1,3-bis-methoxymethyl-benzeneS-Benzyl-Z-acetoxy-1,3-bis-acetoxymethyl-benzene5-Phenoxy-2-hydroxy-1,3-bis-hydroxymethyl-benzene5-Methoxycarbonyl-2-hydroxy-1,3-bis-hydroxymethylbenzeneS-Cumyl-Z-hydroxy-1,3-bis-methoxymethyl-benzeneS-Methylmercapto-Z-hydroxy-1,3-bis-hydroxymethylbenzeneS-Ethoxy-Z-hydroxy-1,3-bis-methoxymethyl-benzene5-Fluoro-2-hydroxy-6-methyl-1,3-bis-hydroxymethylbenzene5-Chloro-2-hydroXy-4,6-dimethyl-1,3-bis-hydroxymethylbenzene5-Chloro-4-hydroxy-2-methyl-1,Z-bis-hydroxymethylbenzene 3,S-Dibromo-2-hydroxy-hydroxymethyl-benzene 2,2'-Dihydroxy-dibenzyletherDihydroxymethyl-hydroquinone 4-Hydroxy-3 ,5-bis-hydroxymethyl-diphenylether2,2-Bis-(4-hydroxy-3,5-bis-hydroxymethyl-phenyl)- propane Bis-(4-hydroxy-5-methyl-3-hydroxymethyl-phenyl)- sulfone 3,4-Dihydroxy-hydroxymethylbenzene2,3-Dihydroxy-1,4-bis-hydroxymethyl-benzene2-Hydroxy-3-methoxy-hydroxymethylbenzene2,2'-Dihydroxy-3,3'-bis-hydroxymethyl-diphenylmethane Compounds BDerived From Thiophenols It is possible to use, instead of the phenolderivatives, the corresponding thiophenol derivatives. But the phenolsare by far superior to the thiophenols since, inter alia, the latter aresubstantially more expensive, have a tendency toward side reactions, andmany of them have an unpleasant smell.

Compounds B Derived From Ethers of Phenols and Thiophenols Suitable are,for example, the alkyl, aralkyl, and aryl ethers of the phenols andthiophenols stated above.

Compounds B Derived From Aromatic Isocyclic and Hetero-Cyclic CompoundsCompounds of Type B of this group of compounds are obtained, forexample, by halogenmethylating the basic structures and then convertingthe halogenmethyl groups to the groups -CH OH, CH O alkyl or CH O acyl.

Numerous halogenmethyl compounds (carrying this group directly in thearomatic nucleus) suitable as intermediate products for the preparationof compounds of the type described here are known.

Compounds of Type B derived from phenolethers also can be obtained byalkylation or aralkylation of the phenolic OH group of phenol alcohols.

Suitable representatives of these groups of compounds are, for example:

1,3-Bis- (3-hydroxymethyl-phenoxy) -propane1,5-Bis-(4-hydroxymethyl-phenoxy)-pentane1,3-Dihydroxymethyl-2-methoxy-S-n-hexyl-benzene1,3-Dihydroxymethyl-2-ethoxy-5-ethyl-benzene 1,3-Dihydroxymethyl-Z-benzyloxy-S-methoxycarbonylbenzene1,3-Dihydroxymethyl-2-methoxy-S-bromo-benzene1,3-Dihydroxymethyl-2-methoxy-S-cumyl-benzene1,3-Dihydroxymethyl-2-cthoxy-S-methylmercaptobenzene 1,3-Dihydroxymethyl-2-ethoxy-5-phenoxy-b enzene 1,3-Dihydroxymethyl-2,5-diethoxy-benzene 1,3 -Dihydroxymethyl-Z-methoxy-S-benzyl-benzene 1,3-Dimethoxymethyl-Z-methoxy-S-fluoro-b enzene 1, 3-Dimethoxymethyl-2-ethoxy-S-methoxy-b enzene 1,3-Dimethoxymethyl-2-methoxy-5-phenyl-b enzene Bis- 2-4-hydroxymethyl-phenoxy) ethyl] ether1,3-Dimethoxymethyl-2-ethoxy-5-bromo-benzene 1,3-Diacetoxymethyl-Z-ethoxy-5-tert.-butyl-benzene1,3-Diacetoxymethyl-Z-methoxy-S-phenylmercaptobenzene 1,3Diacetoxymethyl-2-methoxy-5-chloro-benzene1,3-Diacetoxymethyl-2,S-dimethoxy-benzene 1,3 -Bis-(2-methyl-4-benzyl-6-hydroxymethyl-phenoxy) propane 3,4-Dimethoxy-hydroxymethyl-b enzene 6-Bromo-3,4-dimethoxy-hydroxymethyl-b enzene 4,5-Dimethoxy-Z-methyl-hydroxymethyl-benzene 2,3-Dimethoxy-hydroxymethyl-benzene 2,2'-Dimethoxy-3 ,3'bis-hydroxymethyl-S ,5 '-dimethyldiphenylmethane Dihydroxymethyl-hydroquinonedimethylether 4-Methoxy-3 5-bis-hydroxymethyl-diphenylether Bis-4-ethoxy-5-methyl-3-hydroxymethyl-phenyl sulfone4-Methoxymethyl-diphenylether 2-Hydroxymethyl-diphenylether4,4'-Bis-hydroxymethyl-diphenylether 4,4-Bis-acetoxymethyl-diphenylether4,4'-Bis-methoxymethyl-diphenylether 4,4'-Bis-ethoxymethyl-diphenylether2,4-Bis-methoxymethyl-diphenylether2,4,4-Tris-methoxymethyl-diphenylether 2,4,2-Tris-methoxymethyl-diphenylether2,4,2',4-Tetrakis-methoxymethyl-diphenyletherBis-methoxyrnethyl-4,4'-dimethyl-diphenyletherBis-methoxymethyl-2,4-dimethoxy- S-methyl-diphenyletherBis-methoxymethyl-3,3 '-dimethyl-diphenylsulfideBis-methoxymethyl-2,4-dimethoXy-diphenylsulfide 2, 2'-Dimethyl-4,4'-bis-hydroxym ethyl-diphenylether 4-Chloro--methoxymethyl-diphenylether 1,3 -Bis- (4-methoXymethyl-phen0xy -benzene1,3 -Bis- (4-methoxymethyl-phenoxy) -propane4,4-Bis-methoxymethyl-diphenylsulfide6-Methylmercapto-3-methyl-hydroxymethyl-benzene 2,2-Bis- [4-(4-methoxymethyl-phenoxy -phenyl] -prop ane4,4'-Bis-phenoxymethyl-diphenyletherBis-methoxymethyl-4-phenoxy-diphenylsulfideBis-methoxymethyl-Z-isopropyl-S -methyl-diphenyletherBis-methoxymethyl-3-brom-4-methoxy-diphenylether Bis-methoxymethyl-4-nitr0-diphenylether The preceding compounds contain at least onearomatic ring. The following compounds B also are capable ofcondensation if they contain no aromatic rings.

This group of compounds B is derived from compounds B which contain atleast one substituent which is able to react with an active carbonylcompound with condensation.

Exemplary of such substituents are:

amino groups directly linked to aromatic, particularly to heterocyclicaromatic, rings.

These substituents, of course, also may be linked to aromatic nuclei.

Exemplary of this general group: of compounds are:

Bis-hydroxymethyl-urea Bis-hydroxymethyl-ethyleneureaBis-hydroxymethyl-oxamide Bis-hydroxymethyl-succinic acid diamideBis-methoxymethyl-adipic acid diamide Bis-hydroxymethyl-sebacic aciddiamide Hydroxymethylbenzamide Bis-hydroxymethyl-terephthalic aciddiamide Hydroxymethylbenzenesulfonic acid amide Tetrahydroxymethyl)-melamine Hexa- (methoxymethyl) -melamine The preceding list shows themost important groups of compounds to be used as components B Thepossibilities, however, are not limited thereby; it is also possible touse, for example, the corresponding derivatives of cyanuric acidhydrazides, guanidine derivatives, aminopyrimidines, and the like.

For further possibilities, reference is made to the literatureconcerning condensation resins, e.g. Houben-Weyl, Methoden derorganischen Chemie, 4th edition, volume 14/2, pages 193 to 402,Polyadditions-bzw. Kondensationsprodukte von CarbonylundThiocarbonylverbindungen.

The following examples describe the production of copying materialsaccording to the invention, employing light-sensitive mixed condensates.In spite of their large number, the scope of the present invention is byno means limited thereby.

For better identification of the mixed condensates, in addition to theresult of the elemental analysis, the molecular proportion-calculatedfrom the values obtained by the analysis-is stated in many examples inwhich diazo compound and component B take part in the structure of theproduct. This proportion was calculated under somewhat simplifiedassumptions. Although these statements can not and do not determine theexact structure of the mixed condensates according to the invention,they suflice for identifying condensation products which arereproducible in their characteristics.

As mentioned above, in many cases the condensation conditions, inparticular the quantities employed, are important for furtheridentification. The examples contain all information necessary for thepreparation of the mixed condensates.

In the examples, parts by weight and parts by volume relate to eachother as grams to milliliters. Percentages are by weight if nototherwise stated. The temperatures are degrees Centigrade. In the valuesof the analysis, N means the total nitrogen content and ND the diazonitrogen.

Normally, no great stress was placed on a complete drying of thecondensation products, so that the products obtained may contain smallquantities of water or condensing agent. Moreover, varying quantities ofmetal salts may be entrained in some cases during precipitation.However, the contents of the products of active substance can be easilydetermined by the values of the analysis.

The term crude condensate used in the examples means, generally, thecrude condensation mixture obtained during condensation, which normallyalso contains the condensing medium.

IFOI better orientation, the diazo compounds A(D) and the components Bused for the preparation of the mixed condensates contained in thereproduction material according to the invention are listed in thefollowing Table 1 by numbers. In the examples, reference is made tothese numbers.

TABLE -1 Diazo Compounds Diazo 1: Diphenylamine-4-diazonium salt Diazo2: 3-Methoxy-diphenylamine-4-diazonium salt Diazo 3:4-Methoxy-diphenylamine-4-diazonium salt 27 Diazo 4:2-Carboxy-diphenylamine-4-diazonium salt Diazo 5:2,4,S-Triethoxy-diphenyl-4-diazonium salt Diazo 6: 4(4-Methyl-phenylrnercapto)-2,5-dimethoxybenzene diazonium salt Diazo 7:2,S-Dimethoxy-4-phenoxy-benzene diazonium 28 No. 18: Benzhydrol No. 19:1,4-Bis-(a-hydroxybenzyl)-benzene 'No. 20:1,3-Diisopropyl-4,6-di-methoxymethyl-benzene 'No. 21:4,4-Di-methoxymethyl-diphenylsulfide No. 22:Methoxymethyl-diphenyl-ether, obtained by resalt action of technicalchloromethylated diphenyl-ether Diazo 8: 4 (2,5Diethoxy-benzoylamino)-2,5-diethoxywith sodium methylate (compositionsee Example 53) benzene diazonium salt No. 23:2,2'-Bis-(4-hydroxymethyl-phenoxy)-diethylether Diazo 9:3-Methoxy-diphenyleneoxide-2-diazonium salt No. 24:1,3-Bis-(4-hydroxymethyl-phenoxy)-propane Diazo 4 [NMethyl-'N-naphthyl-(1)-methylamino]- 10 No. 25:Bis-methoxy'methyl-diphenylene oxide benzene diazonium salt N0. 26:4,4-Bis-methoXymethyl-diphenylmethane Diazo 11:4-DiaZo-diphenylamine-3-carb0xylic acid (in- No. 27: Methoxymethylatedbiphenyl ner salt) N0. 28: Methoxymethylated 4,4-dimethyl-diphenylether1311120 121 Dimethoxy 4 y 'p y No. 29: Methoxyrnethylated2-isopropyl-5-methyldimercaptoacetylamino)-benzene diazonium saltphenypther 135 4 [N M y fi- No. 30: Methoxymethylated3-bromo-4-methoxydiphenylam1no]-benzene diazonium salt ether ComponentsB N0. 31: Methoxymethylated dibenzo-thiophene No. l:N,N'-Dimethylol-succinic acid diamide 32: Methgymethyhted henoxybenzeneNo. 33: 2,6-B1s-(methoxymethyl)-4-methyl-phenol No. 2.Hexa-methoxymethyl-melam1ne NO 3: N,N, Dimethylol urea No. 34: 4,4-B1s-(ethoxymethyl)-d1phenylether No. 4: N,N'-Dimethylol-terephthalicacid diamide 353 4,4131?-(hydroxymethyl)dwhenylflher No. 5:2,6-Dimethylol-4-methyl-phenol 1N,N y a No. 6:2,6-Dimethylol-4-methyl-anisole No. 37: N,'N-D1methylol adipic aciddlamldc N0. 7: Di-hydroxy-methyl-durene N0. 38: Trimethylolcitramide.N0. 8: Di-acetoxymethyl-durene No. 9:1,3-Dimethyl-4,6-dimethylol-benzene Examples 1 to 21 No. 10: 1,3-Di'soro l-4,6-dimeth lol-benzene NO. 11: 1 5 Di lacto;methylmaphfhalene Inthe following examples, the good to excellent oleo- 12: 1:4 Dimethy1o1benZene philic properties of the exposure products of 20 of the 13:Commercial bis methoxymethyl diphenylether novel condensation products,when applied to superficially (Composition Stated in Example 8)saponified cellulose acetate film, are shown in combina 14; 4 4' i h ltion with an improved light-sensitivity, in comparison No. 15:4,4'-Di-Ineth0xymethyl-diphenylether with pure formaldehyde condensates.The compositions of No. 16: 2,5-Di-ethoxymethyl-thiophene thecondensation products and of the coating solutions No. 17: 9,lO-Di-methoxymethyl-anthracene used are listed in the following Table 2.4

TABLE 2 Mixed condensate (MC) Coating solution Diazo compound Compo-Proportion of .A(D) Percent Ex. A(D).l nent B1 CHZO Separated asto B1111MC (approx) MC Further additives Solvent ZnCl: 1 Diazo 3, H804- 4 C1--C:N=23.6:5- 1.2 EGMME/DMF/ 2 Diazo 2, H2PO4.. 5 HzPOF-HzPO; 1: 1.IH'zO/CgH OH 3 Diazo 2, H804" 7 C1- 1:1.1 1.0 EGMME 4 do 6 o1- 1:1.1 1.0H 0 5 Diazo 1, BS04- 9+11 Cl- Excess of 9.6 C atoms 0.8 H2O per N2group.

6 Diazo 2, H804- 10 01- 1:2.4 1.65 EGMME 7 Diazo 4,112104 s C1- 1:1.11.0 EGMME 8 Diazo 2, H804 13 Cl- Excess of 10.6 C atoms 1.0 R20 per N agroup.

9 Diazo1,HSOr 19 cl- 1:0.71fl 0.92 EGMME 10 .-do 1s 01- 1:0.@ 0.5 EGMME11. Diazo 2, H804" 13 Crude con- 1:0. 2 2.0 H10 densate 2 1 1 12..---Diazo 2, HSOr 10 c1- 1 1 05 (a) O hlfggriifii H2O (b) 0. 1-.-. moleculeof ZnClz/ H2O dlazo group.

ZnClz 13. Diazo 1, H Cl" 2 0.1 H20 14"... Diazo l, HzPOr plus 16HzPOF-H3PO4 1:2 1.2 H2O dlazo 2, HzPOr.

ZIlClz ZnCIz 15 Diazo 7, Cl--- 20 01- 2 1:1. 2.0 H20 SameasabwesammbWe-m --{3:31::::1::1::::::::::::::::::::::: E28

TABLE 2Continued Mixed condensate (MC) Coating solution Diazo compoundCompo- Proportion of .A(D) Percent Ex. A(D)n nent B; 01120 Separatedasto B1 in MO (approx.) MC Further additives Solvent ZnCl2 17.-." Diazo8, Cl-- 12 rl 1:0.4 2.0 H20 ZIlClz ZnClz 1a..-. Diazo 9, 01-. 12 o1- 21:0. 625- 1.0

19 Diazo 2,-Ol-. C1- 125. 4 (See preparation)-. 1.0 or 0.1 H 0 Z110];ZnClz 2o Diazo a, Cl-- 12 2 1:0.7 1or 0.1- H 0 21 Diazo 2, Hso,- 15 Cl-Excess of 17 C atoms 1. 0 H 0 per N 2 group.

NorE.--EGMME:Ethy1ene glycol monomethyl ether; DMFzDimethyl forrnamide.In the case of purely aqueous coating solutions, coata 0.1 percent byweight solution of the corresponding ing may be eifected by swabbing,whereas solutions predominantly containing organic solvents are appliedby means of a plate whirler. Warm air is used for drying. Afterimage-wise exposure under a negative original, the material isdeveloped, e.g. by wiping over with water or one of the known bufferedsolutions of water-soluble coupling components, e.g. those of thepyrazolone series. The material is then inked up with greasy ink, withthe exposure products accepting the ink. In a number of cases, it isalso possible to reinforce the image by means of lacquers, e.g. theusual emulsion lacquers. In all cases, the oleophilic properties of theexposure products of the novel diazo condensates are superior to thoseof the hitherto known formaldehyde condensates of the correspondingdiazo compounds.

This fact is illustrated by the following comparisons:

Formaldehyde condensates of Diazo Compounds 1 and 2, produced inphosphoric acid as described in Example 1 of US. Pat. No. 3,311,605 andExample 1 of US. Pat. No. 3,406,159, respectively, yield exposureproducts which have only poor ink receptivity or accept no ink at all,when they are coated and processed as described above.

By adding phosphoric acid to the coating solution, even poorer resultsare obtained.

In contradistinction thereto, the novel condensation products producedin phosphoric acid, e.g. those of Examples 2 to 4, 6, 8, 10, 14, 19, and21, possess good to excellent ink receptivity in the image areas. Thegood oleophilic properties are not lost by the addition of phosphoricacid to the coating solutions. The coating solutions used in Examples 3to 15, e.g., can contain 2 molecules of phosphoric acid per diazo group,without a significant reduction of the ink receptivity of the exposureproducts. In Example 21, there are 10 molecules of phosphoric acidpresent per diazo group. A similar effect is also indicated by Example18 in which a crude condensate produced in phosphoric acid is used forcoating without separation of the condensing agent.

It is also demonstrated in these examples that the incorporation ofsmall amounts of component B is suflicient to cause an appreciableefiect according to the invention. This effect occurs even in the caseof an incorporation of only 0.15 mole of component B per mole of diazocompound, although optimum results are not obtained in this case.

Examples 12, 13, 16, and 19 show the superiority of the novelcondensation products as compared with the formaldehyde condensatesprepared in sulfuric acid and precipitated in the form of the zincchloride double salt, which latter are preferred at present as diazoresins. Even with 0.1 percent by weight solutions of the novel mixedcondensates (Example 12) and the addition of 2 molecules of phosphoricacid per diazo group, printing forms of good ink receptivity areobtained from which prints can be made on conventional offset presses.When using formaldehyde condensate (Example 13) and processing in thesame manner, no significant ink receptivity is achieved. A moderatelysatisfactory ink receptivity is achieved only by increasing theconcentration of this diazo compound to many times this quantity.

The preparation and composition of the mixed condensates used inExamples 1 to 21 is described in detail below:

Example 1 17.75 parts by weight of 4-methoxy-diphenylamine-4'- diazoniumsulfate (91%) (Diazo 3, sulfate, Table l) are dissolved in parts byvolume of 86% phosphoric acid. 11.2 parts by weight of dimethylolterephthalic acid diamide (Component B No. 4, Table 1) are introduced inthe form of a fine powder into the solution, with vigorous stirring, andcondensation is eifected for 21 hours at room temperature. The crudecondensate is dissolved in 1,000 parts by volume of water at 40 C. andthe condensation product is then precipitated from the solution byadding 200 parts by volume of 50% zinc chloride solution. The doublesalt is separated, dissolved in 500 parts by volume of water at 50 C.,and reprecipitated by adding zinc chloride. Yield: 26.8 parts by weight.(C 46.6% N 11.5% According to analysis, the product contains theelements N and C in a proportion of 5223.6.

Example 2 6.5 parts by Weight of 3-methoxy-diphenylamine-4-diazoniumphosphate (Diazo 2, phosphate, Table 1) are dissolved in 60 parts byvolume of 86.7% phosphoric acid at 40 C. The solution is cooled down toroom temperature and a solution of 3.4 parts by weight of 2,6-dimethylol-4-methylphenol (Component B No. 5, Table 1) in 7 parts by volume ofN-methylpyrrolidone is rapidly added, while stirring. The mixture iscooled to such an extent that the temperature of the mixture does notexceed 50 C. The mixture is then condensed for 2 hours at 40 C. A crudecondensate soluble in water without any residue is obtained. Forprecipitating the condensation product, the crude condensation mixtureis stirred into 1,000 parts by volume of isopropanol, the precipitate isfiltered with suction, washed twice with 200 parts by volume ofisopropanol, and dried. Yield: 7.5 parts by weight. The acid phosphateof a condensate is obtained which, according to analysis, has an excesscontent of about 9 carbon atoms per diazo group, as compared to theuncondensed diazo compound. About 1 mole of the sec- 0nd component isthus condensed per mole of diazo compound. (C 47.3%, N 7.6%, ND 5.1%, P9.4%; atomic ratio: 2l.7:3:2:1.67.)

Example 3 32.3 parts by weight ot 3-methoxy-diphenylamine-4-di azoniumsulfate (Diazo 2, sulfate, Table 1) are dissolved 31 in 100 parts byvolume of 86% phosphoric acid. 19.4 parts by weight ofbis-(hydroxymethyl)-durene (Component B No. 7, Table 1) are added, withstirring, in small portions at room temperature and condensation isperformed for 25 hours at room temperature.

The crude condensate is dissolved in 1,000 parts by volume of water, asomewhat turbid solution being obtained, which is clarified by pressurefiltration. The chloride of the condensation product is precipitated byheating the filtrate to 70 C. and adding 220 parts by volume ofhydrochloric acid (36% hydrochloric acid diluted with the same volume ofwater). For purification, precipitation is repeated in the same manner.Yield: 33.8 parts by weight. According to analysis, the condensationproduct has an excess content of about 13 carbon atoms per diazo group,as compared to the uncondensed diazo compound. This corresponds to aratio of about 1.1 moles of second component per mole of diazo compound.(C 65.0%, N 8.7%, CI 9.2%; atomic ratio: 26.l:3:1.25).

Example 4 17.8 parts by weight of 3-methoxy-diphenylamine-4- diazoniumsulfate (Diazo 2, sulfate, Table 1) are dissolved in 55 parts by volumeof 86% phosphoric acid. 10 parts by weight of finely powdered4-methyl-2,6-bis- (hydroxymethyl)-anisole (Component B No. 6, Table 1)are then slowly added with stirring. Stirring is continued for 5 hoursat room temperature and for 8.5 hours at 40 C., and the mass is thenleft standing for 30 hours at room temperature. The condensation mixtureis dissolved in 300 parts by volume of water (clear solution) and thecondensate is precipitated with stirring at +5 C. with 150 parts byvolume of saturated common salt solution. The precipitate is separatedand reprecipitated in the same manner. 18.7 parts by weight of a stickycondensation product are obtained which, according to analysis, has anexcess content of 11.2 carbon atoms per diazo group, as compared withthe uncondensed diazo compound. This corresponds to a ratio of about 1.1moles of second component per mole of diazo compound. This correspondsto a ratio of about 1.1 moles of second component per mole of diazocompound. (C 60.3%, N 8.7%, Cl 10.2%; atomic ratio: 24.2:3z3zl38.)

Example 5 15.42 parts by weight of diphenylamine-4-diazonium sulfate(95%) (Diazo l, sulfate, Table 1) are dissolved in 100 parts by volumeof methane sulfonic acid (90% 6.8 parts by weight of finely powdered1,5-bis-(acetoxymethyl)-naphthalene (Component B No. 11, Table 1) arethen added while stirring. After condensing for 1.5 hours at roomtemperature, the crude condensate is capable of forming a clear solutionin water. 4.15 parts by weight of 1,3-dimethyl-4,6-dimethylol-benzene(Component B No. 9, Table 1) are then introduced into the mixture, withstirring, and condensation is continued for another 45 minutes at roomtemperature. The crude condensate is dissolved in 500 parts by volume ofwater (clear solution). The condensation product is preciptated at C. bythe addition of 200 parts by volume of hydrochloric acid (36.5% aciddiluted with the same volume of water). For purification, the product isdissolved in water and again precipitated, as the chloride, by theaddition of hydrochloric acid. Yield: 14.5 parts by weight.

According to analysis, the condensation product has an excess content of10.7 carbon atoms per diazo group, as compared to the uncondensed diazocompound. (C 67.2%, N 10.4%; atomic ratio: 22.613.)

Example 6 32.4 parts by weight of 3-methoxy-diphenylamine-4- diazoniumsulfate (Diazo 2, sulfate, Table l) are dissolved in 320 parts by volumeof 86% phosphoric acid. At an initail internal temperature of 25 C.,44.5 parts by weight of 1,3-diisopropyl-4,6-dimethylol-benzene(Component. B;, No. 10, Table 1) in a very finely powdered form areintroduced, with stirring. Stirring is continued for 1 hour withoutheating and condensation is then performed for 20 hours at +40 C. Acrude condensate is obtained which forms a clear solution in water.

The condensation product is preciptated from the aqueous solution of thecrude condensate by means of hydrochloric acid, again dissolved in waterfor purification, and reprecipitated with hydrochloric acid. Yield: 64parts by weight. (C 68.2%, N 5.1%; atomic ratio: 46.8:3.) It can beassumed, from the result of analysis, that about 2.4 moles of secondcomponent are incorporated per mole of diazo compound.

Example 7 At room temperature and While stirring, 2.8 parts by weight ofbis-(acetoxymethyl)-durene (Component B No. 8, Table l) are cautiouslyadded to a solution of 3.4 parts by weight of 2-carboxydiphenylamine 4diazonium phosphate (Diazo 4, phosphate, Table 1) in 20 parts by volumeof methane sulfonic acid, and stirring is continued for 24 hours at roomtemperature. In order to isolate the reaction product, the clearcondensation mixture is stirred into 250 parts by volume of water. Theprecipitate is drawn off by suction, washed with 250 parts by volume ofwater, again dissolved at 50 C. and reprecipitated by adding 50 parts byvolume of 18% hydrochloric acid. Filtration of the precipitate isimproved by heating the suspension briefly to 80 C. and again cooling.The product is drawn 01? by suction, washed with 1 N hydrochloric acid,and dried at 35 C. The yield is 3.7 parts by weight. (C 64.0%, N 8.5%;atomic ratio: 26.323.) According to analysis, the mixed condensatecontains about 1.1 moles of the second component per mole of diazocompound.

Example 8 33.2 parts b yweight of 3-methoxy-diphenylamine-4- diazoniumsulfate (Diazo 2, sulfate, Table 1) (97.5%) are dissolved in parts byvolume of 86% phosphoric acid. During 15 minutes, 25.9 parts by weightof methoxymethyl-diphenyloxide (for composition, see below) (Component BNo. 13, Table l) are added dropwise, while stirring. A clear crudecondensate is obtained which is stirred for another 1.5 hours at roomtemperature and then for 6 hours at 40 C. The condensate is dissolved in500 parts by volume of water and the solution is cleared of a slightturbidity by filtration. The condensation product is precipitated bymeans of hydrochloric acid. Common salt also may be used forprecipitation. If a product is to be obtained which is substantiallyfree from phosphoric acid, it is advisable to reprecipitate the productin the same manner. Yield: 37.6 parts by weight. According to analysis,the condensation product has a content of 16 more carbon atoms per diazomolecule than does the uncondensed diazo compound. (C 61.7%, N 7.4%, Cl9.3%; atomic ratio: 29.2:3:l.5.)

The methoxymethyl-diphenyloxide used has the following composition:

Percent Diphenylether 1.3 Mono-o- (methoxymethyl) -diphenylether 2.2Mono-p-(methoxymethyl)-dipheny1ether 11.8 Unknown similarmonomethoxymethyl component 3.9 o,p-di-(Methoxymethyl)-diphenylether21.9 p,p'-di-(Methoxymethyl)-diphenylether 47.3tri-(Methoxymethyl)-diphenylether 1.3tetra-(Methoxymethyl)-diphenylether 9.5

When introducing methoxymethyl-diphenyloxide into the acid in theabsence of a diazo compound, it initially dissolves, with vigorousstirring. After a few seconds to a few minutes, a condensateprecipitates which is insoluble in the acid and in boiling water.

A mixed condensate yielding exposure products having the same oleophilicproperties is obtained by replacing the 33 sulfate of Diazo 2 by anequimolecular quantity of the sulfate of Diazo l, in an otherwiseidentical process. However, the mixed condensate containing the Diazo 2yields repreduction layers of better storability.

Example 9 4.65 parts by weight of diphenylamine-4-diazonium sulfate(Diazo 1, sulfate, Table 1) (95%) are dissolved in 600 parts by volumeof 85% phosphoric acid. Then 4.65 parts by weight of1,4-bis-(a-hydroxybenzyD-benzene (Component B No. 19, Table 1) aredissolved in 30 parts by volume of glacial acetic acid which issufficiently heated to cause solution. The hot acetic acid solution isthen poured into the diazo solution while agitating vigorously.Condensation is effected at room temperature over a period of 21 hours.The condensation mixture is then dissolved in 2,000 parts by volume ofwater, filtered until clear, and precipitated by adding 300 parts byvolume of concentrated hydrochloric acid. The precipitate is separated,dissolved at 60 C. in 500 parts by volume of water, filtered, andprecipitated by adding 50 parts by volume of 6 N hydrochloric acidsolution in water. The product which precipitates is reprecipitated oncemore in the same manner. 4.8 parts by weight of the chloride of thecondensation product are thus obtained. According to analysis, theproportion of C:N:Cl is 26.6:3:l.05. This corresponds to a ratio ofabout 0.73 mole of the second component per mole of diazo compound. (C62.2%, N 9.1%, Cl 8.1%.)

Example 10 30.84 parts by Weight of diphenylamine-4-diazonium sulfate(95%) (Diazo 1, sulfate, Table 1) are dissolved in 1,000 parts by volumeof 86% phosphoric acid. During 1 hour, a solution of 18.4 parts byweight of benzhydrol (Component B No. 18, Table 1) in 200 parts byvolume of glacial acetic acid is then added dropwise, while stirring.Condensation is performed for '24 hours at room temperature. A clearcrude condensate which dissolves in water without residue is obtained.Half of the crude condensate is introduced into 2,500 parts by volume ofwater heated to 40 C. The condensation product initially forms a clearsolution and crystallizes in the form of small flakes upon cooling.Yield: 21.9 parts by weight. (C 56.6%, N 8.1%, P 8.9%; atomic ratio:24.5:3:1.5.)

According to analysis, the condensation product has a content of 12.5more carbon atoms per diazo group than does the uncondensed compound.This corresponds to a ratio of about 1 mole of second component per moleof diazo compound.

The other half of the crude condensate is mixed with 1.5 parts by Weightof paraformaldehyde and condensed for hours at room temperature. Thecrude condensate is dissolved in 2,000 parts by volume of water andcleared of a slight turbidity by filtration. It can be separated inknown manner in the form of the zinc chloride double salt. Yield: 22.9parts by weight. (C 59.9%, N 8.5%; atomic ratio: 2463.)

Example 11 For the preparation of the crude condensate, 11 parts byweight of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate,Table 1) are introduced into 39.9

parts by weight of 86% phosphoric acid and the mixture is cooled to roomtemperature. Then, 5.17 parts by weight of a mixture ofmethoxymethylated diphenylethers of the composition given in Example 8(Component B No. 13,

34 Example 12 For the preparation of the diazo condensation product, 81parts by weight of Diazo 2, sulfate (Table 1) are dissolved in 500 partsby volume of 85 phosphoric acid, 61 parts by weight of1,3-diisopropyl-4,G-dimethylol-benzene (Component B No. 10, Table 1) areintroduced during 15 minutes, and the mass is condensed for 39 hours at40 C. The condensation mixture, which forms a clear solution in water,is then dissolved in 2,500 parts by volume of water and reprecipitatedby adding 500 parts by volume of 18% aqueous hydrochloric acid solution.After suction filtration and washing with 0.5 N hydrochloric acid, theproduct is dried with air. Yield: 113 parts by weight of the chloride ofthe condensation product. (C 66.2%, N 8.8%; atomic ratio: 26.3:3.) Fromthe re sult of analysis, the condensate contains about 1 mole of secondcomponent per mole of diazo compound.

Example 13 Diazo resin in the form of the zinc chloride double salt, isobtained by condensing equimolecular quantities of Diazo 1, sulfate(Table 1) and formaldehyde in 80% sulfuric acid, analogously to theprocess described in US. Pat. No. 2,063,631.

Example 14 4.84 parts by weight of 3-methoxy-diphenylamine-4- diazoniumphosphate (Diazo 2, phosphate, Table 1) and 4.4 parts by weight ofdiphenylamine-4-diazonium phosphate (Diazo 1, phosphate, Table 1) aredissolved in 300 parts by volume of 86% phosphoric acid. 6 parts byweight of 2,5-bis-(ethoxy-methyl)-thiophene (Component B No. 16,Table 1) are then added dropwise with vigorous stirring. The mixturebecomes reddish but remains clear. Condensation is performed for 2.5hours at room temperature. The crude condensate forms a clear solutionin water.

For precipitating the reaction product, the mixture is introduced intothoroughly stirred isopropanol at about 65 C. and cooled down to roomtemperature. The precipitate is filtered by suction, thoroughly Washedwith isopropanol and dried. Yield: 10.9 parts by weight. According toanalysis, the condensation product, in the form of an acid phosphate,contains the components 3-methoxy- 4-diaZo-diphenylamine,4-diazo-diphenylamine, and thiophone in a ratio of 0.7 to 0.3 to 2. (C46.9%, N 6.7%, S 10.1%, OCH 3.1%; atomic ratio: 24.6:3:1.98:0.73.)

When introducing the 2,5-bis-(ethoxymethyl)-thiophene into phosphoricacid in the absence of the diazo compound, a homocondensate of thiscompound is immediately formed which is practically insoluble in acidand in water.

Example 15 3.6 parts by weight of 2,5-dimethoxy-4 phenoxy-benzenediazonium chloride (Diazo 7, Table 1) in the form of the double saltwith 0.5 mole of zinc chloride (containing NaCl, N=7.7%) are dissolvedin 60 parts by volume of 93% phosphoric acid. Dry air is passed throughthe solution until no further hydrogen chloride escapes. 2.7 parts byweight of 1,3-diisopropyl-4,6-di-(methoxymethyl)-benzene (Component BNo. 20, Table 1) are then added and the mass is condensed for 1 hour atroom temperature and for 2 hours at 40 C. The condensation mixture isdissolved in water where it forms a clear solution, the condensate isprecipitated with zinc chloride, separated, and dried. Yield: 2.9 partsby weight. (C 57.6%, N 4.4%); atomic ratio: 30.622.) Analysis shows thatthe mixed condensate contains about 1.2 moles of the second componentper mole of diazonium compound.

Example 16 3.6 parts by weight of the diazonium salt used as thestarting material in Example 15 (Diazo 7, zinc chloride double salt,Table 1) are dissolved in 60 parts by volume of 90% methane sulfonicacid and dry air is passed throug the solution until no further hydrogenchloride escapes.

Then, 2.7 parts by weight of 1,3-diisopropyl-4,6-bis-(methoxymethyl)-benzene (Component B No. 20, Table 1) are introduced andthe mass is condensed for one hour at room temperature and for 2 hoursat 40 C.

The mixture is introduced into water and freed from undissolvedcomponents by the addition of charcoal, followed by suction filtration.

The condensation product is precipitated from the filtrate in the formof the zinc cholride double salt. Yield: 5.8 parts by weight. (C 41.0%,N 2.7%; atomic ratio: 35.3:2.) This corresponds to a content ofapproximately 1.5 moles of the second component per mole of diazocompound.

Example 17 1.75 parts by weight of 4-(2,5-diethoxy-benzoylamino)-2,5-diethoxy-benzene diazonium chloride (Diazo 8, Table 1), in the formof the zinc chloride double salt (N=4.8% are dissolved in parts byvolume of 90% methane sulfonic acid, and dry air is passed through themixture until no further hydrogen chloride escapes. Then 0.14 part byweight of 1,4-bis-hydroxymethyl-benzene (Component 13,, No. 12, Table 1)is added. After condensing for 4 hours at room temperature, the mixtureis diluted with water, filtered, and the condensate is precipitated fromthe filtrate by means of a zinc chloride solution. Yield: 2.2 parts byweight. (C 25.2%, N 3.6%; atomic ratio: 24.5:3.)

Example 18 0.78 part by weight of 3-methoxy-diphenylene-oxide-2-diazonium chloride, in the form of the double salt with 0.5 mole of zincchloride (N=7.2%) (Diazo 9, Table 1) is dissolved in 10 parts by volumeof 90% methane sulfonic acid, and dry air is passed through the mixtureuntil no further hydrogen chloride escapes. Then, 0.14 part by weight of1,4-dimethylol-benzene (Component B No. 12, Table 1) is added, andcondensation is effected for 4 hours at room temperature. Thecondensation product is precipitated by means of zinc chloride. Yield:1.4 parts by weight. (C 22.4%, N 2.9%; atomic ratio: 18.2.) Fromanalysis, it can be assumed that about 0.6 mole of the second componentare incorporated per mole of diazo compound.

Example 19 A condensation product is produced from3-methoxydiphenylamine-4-diazoniumchloride and formaldehyde as describedin Example 1 of US. Patent No. 3,406,159 and separated in the form of anacid phosphate which still contains some phosphoric acid (N 9.3%; atomicratio C:N:P=14:3:2.3.)

The product has an average degree of condensation of about 3 units ofmethoxydiphenylamine diazonium salt per molecule, as determined for thediazo amino compound with diisobutylamine in benzene by the cryoscopicmethod for determining molecular weight.

10 parts by weight of the diazo condensation product are dissolved in 85parts by weight of 85% phosphoric acid. 5.7 parts by weight of4,4-bis-methoxymethyl-diphenylether (Component B No. 15, Table 1) areadded dropwise, during 10 minutes, and the mixture is then condensed for20 hours without additional heating. The clear condensation mixture,which forms a clear solution in water, is diluted with 100 parts byvolume of water and then 330 parts by volume of a saturated aqueoussolution of common salt are added. The precipitate thus formed ispurified by dissolving it again in water, reprecipitating it with acommon salt solution, and the precipitated product is then dried. Yield:8.1 parts by weight. (C 48.3%, N 4.3%; atomic ratio: 39.4:3.)

According to analysis, the diazo homocondensate and the second componentare present in the mixed condensate in a molar proportion of about 1:5.4.

Example 20 5 parts by weight of 4-p-tolylmercapto-2,S-dimethoxybenzenediazonium chloride, in the form of the zinc 36 chloride double salt (N6.9%) (Diazo 6, Table 1) are dissolved in 40 parts by volume of sulfuricacid, and dry air is passed through the solution until no furtherhydrogen chloride escapes.

0.88 parts by weight of 1,4-bis-(hydroxymethyl)- benzene (Component BNo. 12, Table 1) is added to the solution in portions, the solution isstirred for 1 hour at room temperature, and is then allowed to standovernight. Thereafter, it is poured into 300 parts by volume of water, 2parts by weight of charcoal are added to remove a slight turbidity, andthe solution is then drawn off by suction. From the clear filtrate, thecondensation product is precipitated by adding zinc chloride and commonsalt. Yield: 5.4 parts by weight, air-dried. (C 31.0%, N 3.5%; atomicratio: 20.6:2.) The condensate contains about 0.7 mole of the secondcomponent per mole of diazo compound.

Example 21 32.3 parts by weight of 3-methoxy-diphenylamine-4- diazoniumsulfate (Diazo 2, sulfate, Table 1) are dissolvel in 265 parts by weightof 93% phosphoric acid. 25.8 parts by weight of4,4'-bis-(methoxymethyl)-diphenylether (Component B No. 15, Table 1) areadded dropwise to the solution and condensation is effective for 2 hoursat 40 C. 16 parts by weight of paraformaldehyde are added to themixture, which yields a clear solution in water, condensation iscontinued for 6 hours at 40 C., and the mixture is then allowed to standovernight. The mixture, which dissolves in water without leaving aresidue, is then dissolved in water and a saturated common salt solutionis added. The voluminous precipitate which forms is maintained at 40 C.for 1 hour, then drawn off by suction as much as possible, and thecontents of the suction filter, i.e. a green paste, are then dried overphosphorus pentoxide, whereupon the product turns into a tough, greenmass which smells strongly of formaldehyde. Yield: 175 parts by weight.(C 16.4%, N 1.9%, S 0.45%, P 13.7%; atomic ratio: C:N:P=30.2:3:9.7.) Ascompared with the uncondensed diazo compound, the condensate has acontent of approximately 17 more C atoms.

Examples 22 to 28 Examples 22 to 28 show that, with the use of the newcondensation products also in the presence of phosphoric acid,reproduction layers are obtained which are substantially less sensitiveto fingerprints during handling than are reproduction layers produced inthe same manner but with the use of the known formaldehyde condensatesof the diazo compounds alone (same anion and same addition of phosphoricacid).

The coating solutions given in Table 3 are applied to an aluminumsupport which has been roughened with metal wire brushes and pretreatedwith polyvinyl phosphonic acid according to U.S. Pat. No. 3,220,832. Thecoating is then dried with hot air.

The decrease of the sensitivity to moisture of the material, whichbecomes noticeable in the sensitivity to fingerprints, naturallyinvolves a decrease in the developability of the reproduction layer withwater. Aqueous solutions of salts, which preferably additionally containwetting agents or small additions of organic solvents, generally aresuitable for development, however.

The developers used in the individual examples are given in the lastcolumn of Table 3, which contains the details of the examples.

Developer I means: parts by volume of water, 5 parts by weight of sodiumlauryl sulfate (50%) (residue sodium sulfate), and 3 parts by weight oftartaric acid.

Developer 11 means: Developer I to which 2 parts by weight of benzylalcohol are added.

The production of the copy shows that the reproduction layers obtainedwith the use of the new condensation products are up to four times aslight-sensitive as are the 37 reproduction layers obtained with the useof the known formaldehyde condensates of the same diazo compounds. Theimage areas accept printing inks very well.

33 (clear solution) and the chloride of the condensation product isprecipitated at 40 C. by dropwise adding 220 parts by volume ofhydrochloric and (36% HCl diluted TABLE 3 Mixed condensate (MC) Coatingsolution Gom- Proportion of Diazo compound ponent Separated in A(D) n toB1 Percent Devel- Ex. )n B; CH the form ofin MO (approx.) MC Otheradditives Solvent oper 22 As in Example 3 0. 5 2 molecules of EGGME IHzPO4 per diazo As in Example 4 EGMME H O As in Example 5 E GMME I As inExample 6 EGMME II As in Example 7 GMME I As in Example 9 0.46 do EGMMEI 28 Diazo 1, H PO H2PO4'H3PO4 1:1. 52 0. 8 1 molecule of H01 EGMME/HZO,II

per diazo group. 96:4 p.b.v.

NoTE.--P.b.v.=parts by volume; EGMME =ethy1eneglycol monomethyl ether.

4.4 parts by weight of diphenylamine-4-diazonium phosphate (Diazo 1,phosphate, Table 1) are dissolved in 300 parts by volume of 96.5%phosphoric acid. A boiling solution of 4.0 parts by weight of9,10-bis-methoxymethyl-anthracene (Component B No. 17, Table 1) in 30parts by volume of glacial acetic acid is poured into the solution, withthorough stirring. Condensation is performed for 1.5 hours withoutfurther heating. The crude condensate is soluble in water without anyresidue. In order to isolate the condensation product, the condensationmixture is diluted with 150 parts by volume of methanol and the solutionis poured, with stirring, into 2,000 parts by volume of isopropanol atabout 65 C. The precipitate is filtered ofi with suction, washed withiso propanol, and dried. Yield: 5.4 parts by Weight. According toanalysis the condensate has a content of 24.4 more carbon atoms permolecule of diazo compound than does the uncondensed diazo compound;this corresponds to about 1.5 moles of second component per mole ofdiazo compound. (C 52.9%, N 5.1%, P 11.3%; atomic ratio: 36.4:323).

The examples below show the wide use of the new condensation products onvarious support materials and in various reprographic processes.

In addition to the advantages of the improved oleophilic properties ofthe exposure products and the improved light-sensitivity, which alsorepeatedly occur in the following examples, these examples show furtheradvantages of individual groups of mixed condensates.

Example 29 An electrolytically roughened aluminum foil is coated byswabbing with a 2% by weight aqueous solution of the chloride of acondensation product prepared from Diazo compound 2 and Component B No.14, Table 1. After image-wise exposure to light through a negative, thefoil is developed by wiping it over with 1.5% aqueous phosphoric acidand inked up with greasy ink. An eflicient printing form is obtained.

A similarly efficient printing form is analogously ob tained by applyingthe same solution to a mechanically grained aluminum foil, which hasbeen pretreated in known manner with an alkali silicate.

Instead of using the chloride of the condensation product, it also ispossible to use the corresponding zinc chloride double salt or cadmiumchloride double salt. De- 'veloper II is suitable for development.

The condensation product is prepared in the following manner:

30.2 parts by weight of 3-methoxy-diphenylamine-4- diazonium-sulfate(Diazo 2, sulfate, Table 1) are dissolved in 93.5 parts by volume of 86%phosphoric acid. 29.3 parts by weight of finely pulverized4,4-bis-acetoxymethyl-diphenylether (Component B No. 14, Table l) arethen added with vigorous stirring, the mixture is stirred for another1.5 hours without heating and finally condensed for 3.5 hours at 40 C.The clear condensation mixture is dissolved in 500 parts by volume ofwater with the same volume of water). For purification, the precipitateis dissolved in warm water and the chloride is again precipitated by theaddition of hydrochloric acid. Drying is performed at 30 C. bycirculating air in a drying chamber. Yield: 38.7 parts by weight. (C65.7%; N 8.1%, Cl, 8.6%; atomic ratio 28.5:3:l.26.)

Example 30 An aluminum foil roughened by means of metal brushes andpretreated with polyvinyl phosphonic acid according to U.S. Pat. No.3,220,832 is coated with the following coating solutions, and the layeris dried:

Diazo-formaldehyde condensate (parts by weight) 0.4 0.04 0.13 Mixedcondensate (parts by weight) 0.34 0.34 0.34 0.31 0.23 Phosphoric acid,moles per mole diazo groups 2.8 0 0.5 2.8 0.5 2.8

Formaldehyde condensate from diazo compound 2, chloride (Table I), in2.8 moles of phosphoric acid, by analogy to Example 1 of U.S. Pat. No.3,406,159.

2 The mixed condensate (chloride) is the same as in Example 29.

Duration of exposure in relative units:

The developer in Case 1 is water, in Cases 2 to 6 Developer II (seeExamples 22 to 28). For the purpose of further increasing the length ofprinting run, it is possible to reinforce the printing formes obtainedin this manner with suitable lacquers, e.g. the products described inU.S. Pats. Nos. 3.313,233, particularly Example 1, and 2,754,279.

After storage for 8 'weeks at 52 C., the presensitized materials 1, 4and 6 still can be easily processed. The layers containing lessphosphoric acid or no phosphoric acid are less storable under theseconditions.

For increasing the printing run of the printing formes produced from thereproduction material, it also is possible to provide the reproductionlayer with a coating of water-insoluble polymers as described, forexample, in U.S. Pat. No. 3,136,637.

It also is possible to further add to such coatings dyestufis, pigments,and diazo compounds, e.g. the com- 39 pounds described in US. Pats. Nos.3,180,732 and 3,175,- 906. A corresponding working method is describedin US. Patent Application Ser. No. 652,024.

As a mixed condensate there also may be used a product prepared from 1mole of 3-methoxy-diphenylamine-4- diazonium sulfate (Diazo 2, sulfate,Table 1) and 1.5 moles of 4,4'-bis-methoxymethyl-diphenylether(Component B No. 15, Table 1) analogously to Example 29 and separated asthe chloride. 'In this case, even shorter exposure times are requiredbut the addition of more phosphoric acid is necessary for achievinglayers of the same storability.

Example 31 The aluminum support used in Example 30, precoated withpolyvinylphosphonic acid, is coated with the following solution:

1.25 parts by weight of a crude condensate of3-methoxy-diphenylamine-4-diazonium chloride and formaldehyde inphosphoric acid (molar ratio 1:1:2.8), condensation for 40 hours at 40C.,

10.0 parts by weight of the condensation product described in Example 8,

5.1 parts by weight of 85% phosphoric acid,

2,400.0 parts by weight of ethylene glycol monomethyl ether, and

580.0 parts by weight of butyl acetate.

The coating is dried for 2 minutes at 100 C.

The sensitivity of the reproduction layer to fingerprints duringhandling is considerably reduced, compared to a reproduction layercontaining only the first-mentioned crude condensate, and thelight-sensitivity of the new reproduction layer is somewhat more thantwice as high as that of a layer containing only the first-mentionedcrude condensate. Development of the exposed reproduction material canbe effected with Developer II described in Examples 22 to 28. Theprinting form then can be lacquered with the conventional lacquers, e.g.those described in the preceding example, and its run thus can befurther increased.

The reproduction material produced according to this example has a verygood storability. Plates stored for three years in the absence of lightat room temperature (not air-conditioned) still can 'be processedaccording to the above method into printable printing formes.

Example 32 A paper printing foil produced according to the disclosure ofUS. Pat. No. 2,778,735, is coated with the following solution, byswabbing, and dried.

Coating solution: 2 parts by weight of the mixed condensation productdescribed in Example 12 are dissolved in 97 parts by weight of warmwater. The solution is reacted with 0.53 part by weight of sodiumsulfite and stirred for one hour. The somewhat turbid solution isdirectly used for coating the support.

After image-wise exposure of the reproduction material and developmentwith water, a very satisfactorily oleophilic image is obtained whichaccepts greasy ink well. The image areas have better oleophilicproperties than have those obtained according to the same working methodusing a commercial diazo resin (diphenylamine-4- diazonium sulfatecondensed in 80% sulfuric acid with formaldehyde and precipitated as thezinc chloride double salt).

EXAMPLE 33 An electrolytically roughened aluminum foil is coated with asolution of the following constituents:

2.0 parts by weight of the diazo condensate described in Example 12,

80.0 parts by volume of water,

0.284 part by weight of zinc chloride,

0.527 part by Weight of sodium sulfite, and

20.0 parts by volume of dimethylformamide.

After image-wise exposure under a line negative, the foil is developedwith Developer II described in Examples 22 to 28, rinsed with water,treated with 1% aqueous phosphoric acid and inked up with greasy ink. Anefiicient printing form is obtained the image areas of which have betteroleophilic properties than have those of a printing form produced in thesame manner using the same derivative of a commercial diazo resin (seeExample 32).

When employing the above coating solution, it also is possible to obtainoffset printing forms on mechanically grained aluminum treated in knownmanner with aqueous alkali silicate solution, with development in thesame manner.

Example 34 A polyethylene terephthalate film roughened by sand blastingis coated with the following finely ground coating mixture and thecoating is dried:

1.25 parts by weight of poly-N-vinyl-N-methylacetamide (K value 91),

0.5 part by weight of Heliogen Blue B powder (CI 0.1 part by weight offinely divided silicon dioxide (Aerosil MOX 170),

0.375 part by weight of the diazo condensate described below,

18.0 parts by weight of water, and

1.6 parts by weight of ethanol.

After image-wise exposure under a negative, a blue colored positivetanned image is obtained by rinsing with water. The diazo condensate isprepared as follows:

32.4 parts by weight of 3-methoxy-diphenylamine-4- diazonium-sulfate(Diazo 2, sulfate, Table 1), are dissolved in 320 parts by volume of 85% phosphoric acid. 16.6 parts by weight of finely pulverized andscreened 1,3-dimethyl-4,G-dimethylol-benzene (Component B No. 9,Table 1) are added, with vigorous stirring, during 10 minutes, andstirring is continued for 30 minutes at room temperature. Condensationis then performed, with stirring, for 42 hours at 40 C. The crudecondensate is soluble in water without any residue.

For separating the condensation product, the condensation mixture isdissolved in 1,000 parts by volume of water, the product is precipitatedby the addition of 60 parts by volume of 45% aqueous hydrobromic acidand the precipitate is filtered off with suction.

For purification, the product is again dissolved in 1,000 parts byvolume of water of 50 C. and the product is again precipitated by theaddition of hydrobromic acid, washed with 1% aqueous hydrobromic acidand the filtered product is air-dried. Yield: 42 parts by weight. (C53.1%, N 7.8%, Br 18.6%; atomic ratio 23.8:3:1.25). About 1.1 moles ofsecond component are present per mole of diazo compound.

Example 35 The same support as in Example 34 is coated with thefollowing mixture:

4.0 parts by weight of polyvinylpyrrolidone (K value 1.0 part by weightof the diazo condensate described in Example 29,

0.1 part by weight of crystal violet (CI 42,555),

12.0 parts by weight of ethanol, and

88.0 parts by weight of water.

After image-wise exposure under a negative, a blue colored pOSllIlVCtanned image is obtained by rinsing with water.

Example 36 An electrolytically roughened aluminum foil is coated withthe coating solution described in Example 35.

After image-wise exposure under a positive, the layer parts not hardenedby the action of light are dissolved

1. A PROCESS FOR THE PREPARATION OF A POLYCONDENSATION PRODUCT OF ANAROMATIC DIAZONIUM COMPOUND WHICH COMPRISES REACTING IN THE ABSENCE OFADDED FORMALDEHYDE AT LEAAST ONE A-N2X COMPOUND AND AT LEAST ONE B1COMPOUND OF THE FORMULA